Laundry care or dish care composition comprising a poly alpha-1,6-glucan derivative

ABSTRACT

A laundry care or dish care composition can include a poly alpha-1,6-glucan derivative, wherein the poly alpha-1,6-glucan derivative includes:(i) a poly alpha-1,6-glucan backbone of glucose monomer units, wherein greater than or equal to 40% of the glucose monomer units are linked via alpha-1,6 glycosidic linkages, and optionally at least 5% of the backbone glucose monomer units have branches via alpha-1,2 and/or alpha-1,3 glycosidic linkages; and(ii) at least one hydrophobic organic group linked to the poly alpha-1,6-glucan backbone through an ether (—O—) linkage moiety;wherein, the poly alpha-1,6-glucan backbone has a weight average degree of polymerization of at least 5;wherein, the poly alpha-1,6-glucan derivative has a degree of substitution of ether linkage moiety of from 0.20 to 1.00;wherein the poly alpha-1,6-glucan derivative is substantially free from hydrophilic substitution.

This application claims benefit of Provisional Ser. No. 63/037,014,filed on Jun. 10, 2020.

FIELD OF THE INVENTION

The present invention is directed towards poly alpha-1,6-glucanderivatives comprising poly alpha-1,6-glucan substituted with at leastone hydrophobic organic group. The hydrophobic organic group linked tothe poly alpha-1,6-glucan through a —O— linkage moiety. The polyalpha-1,6-glucan comprises a backbone of glucose monomer units whereingreater than or equal to 40% of the glucose monomer units are linked viaalpha-1,6 glycosidic linkages, and optionally at least 5% of thebackbone glucose monomer units have branches via alpha-1,2 and/oralpha-1,3 glycosidic linkages.

BACKGROUND OF THE INVENTION

Polysaccharides modified with ether groups may be used for aqueousapplications such as rheology modifiers, emulsion stabilizers, anddispersing agents in cleaning, detergent, cosmetics, food, cement, film,and paper production. For example, carboxymethyl cellulose derivativeshave been used as rheology modifiers. Enzymatically-polymerizedpolysaccharides and their derivatives can have narrow polydispersity andcompositional consistency, offering advantages in some applications.Ether derivatives of poly alpha-1,3-1,6-glucan and methods of using suchmaterials as viscosity modifiers are disclosed in published patentapplication US 2015/0232785. Hydrocolloids and aqueous solutionscomprising a poly alpha-1,3-glucan ether compound and such materials inthe form of a personal care product, pharmaceutical product, foodproduct, household product, or industrial product, are disclosed in U.S.Pat. No. 10,005,850. The pattern of glycosidic linkages in the glucanpolymer backbone, in combination with selected substituents on the ethercompound and the degree of substitution, can affect the solubility ordispersibility of the glucan ether compound in aqueous solution.

There is a continuing need for new materials which can be used inaqueous applications such as laundry and dish care, for example as stainremoval, anti-deposition, anti-graying, and/or whiteness performingagents in laundry detergents, and in dish care applications. Thereremains a need for such materials which can be made from renewableresources and which are biodegradable.

US 2019/202942, US 2020/002646 and US 2019/136153 relate to compositionscomprising polysaccharide derivatives.

SUMMARY OF THE INVENTION

The present invention provides a laundry care or dish care compositioncomprising a poly alpha-1,6-glucan derivative, wherein the polyalpha-1,6-glucan derivative comprises:

-   -   (i) a poly alpha-1,6-glucan backbone of glucose monomer units,        wherein greater than or equal to 40% of the glucose monomer        units are linked via alpha-1,6 glycosidic linkages, and        optionally at least 5% of the backbone glucose monomer units        have branches via alpha-1,2 and/or alpha-1,3 glycosidic        linkages; and    -   (ii) at least one hydrophobic organic group linked to the poly        alpha-1,6-glucan backbone through an ether (—O—) linkage moiety;    -   wherein, the poly alpha-1,6-glucan backbone has a weight average        degree of polymerization of at least 5; and    -   wherein, the poly alpha-1,6-glucan derivative has a degree of        substitution of ether linkage moiety of from 0.20 to 1.00.

DETAILED DESCRIPTION OF THE INVENTION

The disclosures of all cited patent and non-patent literature areincorporated herein by reference in their entirety.

As used herein, the term “embodiment” or “disclosure” is not meant to belimiting, but applies generally to any of the embodiments defined in theclaims or described herein. These terms are used interchangeably herein.

In this disclosure, a number of terms and abbreviations are used. Thefollowing definitions apply unless specifically stated otherwise.

The articles “a”, “an”, and “the” preceding an element or component areintended to be nonrestrictive regarding the number of instances (i.e.occurrences) of the element or component. These articles should be readto include one or at least one, and the singular word form of theelement or component also includes the plural unless the number isobviously meant to be singular.

The term “comprising” means the presence of the stated features,integers, steps, or components as referred to in the claims, but that itdoes not preclude the presence or addition of one or more otherfeatures, integers, steps, components, or groups thereof. The term“comprising” is intended to include embodiments encompassed by the terms“consisting essentially of” and “consisting of”. Similarly, the term“consisting essentially of” is intended to include embodimentsencompassed by the term “consisting of”.

Where present, all ranges are inclusive and combinable. For example,when a range of “1 to 5” is recited, the recited range should beconstrued as including ranges “1 to 4”, “1 to 3”, 1-2”, “1-2 and 4-5”,“1-3 and 5”, and the like.

As used herein in connection with a numerical value, the term “about”refers to a range of +/−0.5 of the numerical value, unless the term isotherwise specifically defined in context. For instance, the phrase a“pH value of about 6” refers to pH values of from 5.5 to 6.5, unless thepH value is specifically defined otherwise.

It is intended that every maximum numerical limitation given throughoutthis specification includes every lower numerical limitation, as if suchlower numerical limitations were expressly written herein. Every minimumnumerical limitation given throughout this specification will includeevery higher numerical limitation, as if such higher numericallimitations were expressly written herein. Every numerical range giventhroughout this specification will include every narrower numericalrange that falls within such broader numerical range, as if suchnarrower numerical ranges were all expressly written herein.

The use of numerical values in the various ranges specified in thisapplication, unless expressly indicated otherwise, are stated asapproximations as though the minimum and maximum values within thestated ranges were both proceeded by the word “about”. In this manner,slight variations above and below the stated ranges can be used toachieve substantially the same results as values within the ranges.Also, the disclosure of these ranges is intended as a continuous rangeincluding each and every value between the minimum and maximum values.

The features and advantages of the present disclosure will be morereadily understood, by those of ordinary skill in the art from readingthe following detailed description. It is to be appreciated that certainfeatures of the disclosure, which are, for clarity, described above andbelow in the context of separate embodiments, may also be provided incombination in a single element. Conversely, various features of thedisclosure that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any sub-combination.In addition, references to the singular may also include the plural (forexample, “a” and “an” may refer to one or more) unless the contextspecifically states otherwise.

As used herein:

The term “polysaccharide” means a polymeric carbohydrate moleculecomposed of long chains of monosaccharide units bound together byglycosidic linkages and on hydrolysis gives the constituentmonosaccharides or oligosaccharides.

The terms “poly alpha-1,6-glucan”, “alpha-1,6-glucan”, “dextran”,“dextran polymer” and the like herein refer to an alpha-glucancomprising at least 40% alpha-1,6 glycosidic linkages.

The terms “percent by weight”, “weight percentage (wt %)” and“weight-weight percentage (% w/w)” are used interchangeably herein.Percent by weight refers to the percentage of a material on a mass basisas it is comprised in a composition, mixture or solution.

The phrase “water insoluble” means that less than 1 gram of thepolysaccharide or polysaccharide derivative dissolves in 1000milliliters of water at 23° C.

The term “water soluble” means that the polysaccharide or polysaccharidederivative is soluble at 1% by weight or higher in pH 7 water at 25° C.The percentage by weight is based on the total weight of thepolysaccharide soluble in water, for example, 1 gram of polysaccharidein 100 grams of water.

The term “hydrophobic” refers to a molecule or substituent which isnonpolar and has little or no affinity for water, and which tends torepel water.

The term “molar substitution” (M.S.) as used herein refers to the molesof a hydrophobic organic group per monomeric unit of the polysaccharideor the derivative thereof. It is noted that the molar substitution valuefor a poly alpha-1,6-glucan derivative, for example, may have a veryhigh upper limit, for example in the hundreds or even thousands. Forexample, if the hydrophobic organic group is a hydroxyl-containing alkylgroup, via the addition of ethylene oxide to one of the hydroxyl groupsof the poly alpha-1,6-glucan, then the so-formed hydroxyl group from theethylene oxide can then be further etherified to form a polyether.

The molecular weight of a polysaccharide or polysaccharide derivativecan be represented as statistically averaged molecular massdistribution, i.e. as number-average molecular weight (M_(n)) or asweight-average molecular weight (M_(w)), both of which are generallygiven in units of Daltons (Da), i.e. in grams/mole. Alternatively,molecular weight can be represented as DPw (weight average degree ofpolymerization) or DPn (number average degree of polymerization).Various means are known in the art for calculating these molecularweights from techniques such as high-pressure liquid chromatography(HPLC), size exclusion chromatography (SEC), gel permeationchromatography (GPC), and gel filtration chromatography (GFC).

As used herein, “weight average molecular weight” or “M_(w)” iscalculated as

M_(w)=ΣN_(i)M_(i) ²/ΣN_(i)M_(i); where M_(i) is the molecular weight ofan individual chain i and N_(i) is the number of chains of thatmolecular weight. In addition to using SEC, the weight average molecularweight can be determined by other techniques such as static lightscattering, mass spectrometry especially MALDI-TOF (matrix-assistedlaser desorption/ionization time-of-flight), small angle X-ray orneutron scattering, and ultracentrifugation.

As used herein, “number average molecular weight” or “M_(n)” refers tothe statistical average molecular weight of all the polymer chains in asample. The number average molecular weight is calculated asM_(n)=ΣN_(i)M_(i)/ΣN_(i) where M_(i) is the molecular weight of a chaini and N_(i) is the number of chains of that molecular weight. Inaddition to using SEC, the number average molecular weight of a polymercan be determined by various colligative methods such as vapor pressureosmometry or end-group determination by spectroscopic methods such asproton NMR, FTIR, or UV-vis.

As used herein, number average degree of polymerization (DPn) and weightaverage degree of polymerization (DPw) are calculated from thecorresponding average molecular weights Mw or Mn by dividing by themolar mass of one monomer unit M₁. In the case of unsubstituted glucanpolymer, M₁=162. In the case of a substituted glucan polymer,M₁=162+M_(f)×DoS, where M_(f) is the molar mass of the substituent groupand DoS is the degree of substitution with respect to that substituentgroup (average number of substituted groups per one glucose unit).

Glucose carbon positions 1, 2, 3, 4, 5 and 6 as referred to herein areas known in the art and depicted in Structure I:

The terms “glycosidic linkage” and “glycosidic bond” are usedinterchangeably herein and refer to the type of covalent bond that joinsa carbohydrate (sugar) molecule to another group such as anothercarbohydrate. The term “alpha-1,6-glucosidic linkage” as used hereinrefers to the covalent bond that joins alpha-D-glucose molecules to eachother through carbons 1 and 6 on adjacent alpha-D-glucose rings. Theterm “alpha-1,3-glucosidic linkage” as used herein refers to thecovalent bond that joins alpha-D-glucose molecules to each other throughcarbons 1 and 3 on adjacent alpha-D-glucose rings. The term“alpha-1,2-glucosidic linkage” as used herein refers to the covalentbond that joins alpha-D-glucose molecules to each other through carbons1 and 2 on adjacent alpha-D-glucose rings.

The term “alpha-1,4-glucosidic linkage” as used herein refers to thecovalent bond that joins alpha-D-glucose molecules to each other throughcarbons 1 and 4 on adjacent alpha-D-glucose rings. Herein,“alpha-D-glucose” will be referred to as “glucose”.

The glycosidic linkage profile of a glucan, dextran, substituted glucan,or substituted dextran can be determined using any method known in theart. For example, a linkage profile can be determined using methods thatuse nuclear magnetic resonance (NMR) spectroscopy (e.g., ¹³C NMR or¹HNMR). These and other methods that can be used are disclosed in FoodCarbohydrates: Chemistry, Physical Properties, and Applications (S. W.Cui, Ed., Chapter 3, S. W. Cui, Structural Analysis of Polysaccharides,Taylor & Francis Group LLC, Boca Raton, Fla., 2005), which isincorporated herein by reference.

The structure and molecular weight of a polysaccharide or polysaccharidederivative can be determined based on the reactants and confirmed byvarious physiochemical analyses known in the art to include but notlimited to multiangle light scattering diffraction mass spec (MALDI) andsize exclusion chromatography (SEC). Degree of substitution of apolysaccharide or polysaccharide derivative can be determined by variousphysiochemical analyses known in the art to include but not limited toNMR spectroscopy and chemical digest methods.

The present invention provides a laundry care or dish care compositioncomprising a poly alpha-1,6-glucan derivative, wherein the polyalpha-1,6-glucan derivative comprises:

-   -   (i) a poly alpha-1,6-glucan backbone of glucose monomer units,        wherein greater than or equal to 40% of the glucose monomer        units are linked via alpha-1,6 glycosidic linkages, and        optionally at least 5% of the backbone glucose monomer units        have branches via alpha-1,2 and/or alpha-1,3 glycosidic        linkages; and    -   (ii) at least one hydrophobic organic group linked to the poly        alpha-1,6-glucan backbone through an ether (—O—) linkage moiety;    -   wherein, the poly alpha-1,6-glucan backbone has a weight average        degree of polymerization of at least 5;    -   wherein, the poly alpha-1,6-glucan derivative has a degree of        substitution of ether linkage moiety of from 0.20 to 1.00; and    -   wherein, the poly alpha-1,6-glucan derivative is substantially        free from hydrophilic substitution.

The poly alpha-1,6-glucan derivative comprises:

-   -   (i) a poly alpha-1,6-glucan backbone of glucose monomer units,        wherein greater than or equal to 40% of the glucose monomer        units are linked via alpha-1,6 glycosidic linkages, and        optionally at least 5% of the backbone glucose monomer units        have branches via alpha-1,2 and/or alpha-1,3 glycosidic        linkages; and    -   (ii) at least one hydrophobic organic group linked to the poly        alpha-1,6-glucan backbone through an ether (—O—) linkage moiety;    -   wherein, the poly alpha-1,6-glucan backbone has a weight average        degree of polymerization of at least 5;    -   wherein, the poly alpha-1,6-glucan derivative has a degree of        substitution of ether linkage moiety of from 0.20 to 1.00; and    -   wherein, the poly alpha-1,6-glucan derivative is substantially        free from hydrophilic substitution.

The poly alpha-1,6-glucan derivatives disclosed herein comprisewater-soluble poly alpha-1,6-glucan comprising a backbone of glucosemonomer units wherein greater than or equal to 40% of the glucosemonomer units are linked via alpha-1,6-glycosidic linkages, andoptionally at least 5% of the backbone glucose monomer units havebranches via alpha-1,2 and/or alpha-1,3-glycosidic linkages.

Typically, the poly alpha-1,6-glucan being randomly substituted withhydrophobic organic groups on the polysaccharide backbone and/or on anybranches which may be present, such that the poly alpha-1,6-glucanderivative comprises, in some aspects, unsubstituted and substitutedalpha-D-glucose rings. As used herein, the term “randomly substituted”means the substituents on the glucose rings in the randomly substitutedpolysaccharide occur in a non-repeating or random fashion. That is, thesubstitution on a substituted glucose ring may be the same or different[i.e. the substituents (which may be the same or different) on differentatoms in the glucose rings in the polysaccharide] from the substitutionon a second substituted glucose ring in the polysaccharide, such thatthe overall substitution on the polymer has no pattern. Further, thesubstituted glucose rings occur randomly within the polysaccharide(i.e., there is no pattern with the substituted and unsubstitutedglucose rings within the polysaccharide).

In some embodiments, depending on reaction conditions and the specificsubstituent used to derivatize the poly alpha-1,6-glucan, the glucosemonomers of the polymer backbone may be disproportionately substitutedrelative to the glucose monomers of any branches, including branches viaalpha-1,2 and/or alpha-1,3 linkages, if present. In another embodiment,the glucose monomers of the branches, including branches via alpha-1,2and/or alpha-1,3 linkages, if present, may be disproportionatelysubstituted relative to the glucose monomers of the polymer backbone. Insome embodiments, depending on reaction conditions and the specificsubstituent used, substitution of the poly alpha-1,6-glucan may occur ina block manner.

In some embodiments, depending on reaction conditions and the specificsubstituent used to derivatize the poly alpha-1,6-glucan, it is possiblethat the hydroxyl groups at certain glucose carbon positions may bedisproportionately substituted. For example, in some embodiments, thehydroxyl at carbon position 2, 3, or 4 may be more substituted than thehydroxyls at other carbon positions.

The poly alpha-1,6-glucan derivatives disclosed herein comprise polyalpha-1,6-glucan substituted with at least one hydrophobic organicgroup, wherein the at least one hydrophobic organic group or groups areindependently linked to the poly alpha-1,6-glucan polysaccharidebackbone and/or to any branches through a linkage moiety selected from—O— (ether).

In addition to the hydrophobic organic groups that linked to the polyalpha-1,6-glucan through —O— linkage moiety, the poly alpha-1,6-glucanderivatives disclosed here in may further comprise additionalhydrophobic organic groups linked to the poly alpha-1,6-glucan, ifpresent, through a linkage moiety selected from —OCO—(ester),—OSO₂—(sulfonyl), —OCOO—(carbonate), or

(carbamoyl or carbamate, also referred to as urethane).

Further, the poly alpha-1,6-glucan derivatives disclosed here aresubstantially free from of hydrophilic group modifications. Bysubstantially free it is typically meant the derivatives are notdeliberately substituted. However, very minor amounts of substitutionse.g. due to impurities or by-products from hydrophobic substitutionreactions are allowed.

Further, the poly alpha-1,6-glucan derivatives disclosed here in mayfurther comprise other functional groups as modification.

In typical aspects, the at least one hydrophobic organic group canderivatize the poly alpha-1,6-glucan at the 2, 3, and/or 4 glucosecarbon position of a glucose monomer on the backbone of the glucan,and/or at the 2, 3, 4, or 6 glucose carbon position(s) of a glucosemonomer on a branch, if present. At unsubstituted positions, a hydroxylgroup is present in a glucose monomer.

In one embodiment, the at least one hydrophobic organic group comprisesa C₁ to C₁₈ alkyl, a C₂ to C₁₈ alkenyl, a C₂ to C₁₈ alkynyl, a polyethercomprising repeat units of (—CH₂CH₂O—), (—CH₂CH(CH₃)O—),(—CH(CH₃)CH(CH₃)O—), (—CH₂CH(CH₂CH₃)O—), or a mixture thereof, whereinthe total number of repeat units is in the range of from 2 to 100, a C₆to C₂₀ aryl, a benzyl, a C₁-C₁₈ alkyl sulfonyl, a C₆-C₂₀ aryl sulfonyl,a p-toluenesulfonyl group, or any combination thereof. A suitablehydrophobic organic group is a polyether comprising repeat units ofC₃-C₁₈ alkoxylate.

In another embodiment, the at least one hydrophobic organic groupcomprises a C₁ to C₁₈ alkyl, a benzyl, a p-toluenesulfonyl group, or anycombination thereof. In yet another embodiment the at least onehydrophobic organic group comprises a benzyl group, and the benzyl groupis further substituted with one or more of a halogen, a cyano, an ester,an amide, an ether group, a C₁ to C₆ alkyl group, an aryl group, a C₂ toC₆ alkenyl group, a C₂ to C₆ alkynyl group, or any combination thereof.

In one embodiment, at least one hydrophobic organic group comprises a C₁to C₁₈ alkyl group, a hydroxy alkyl group, a C₂ to C₁₈ alkenyl group, aC₂ to C₁₈ alkynyl group, a benzyl group, a C₆ to C₂₀ aryl group, apolyether comprising repeat units of (—CH₂CH₂O—), (—CH₂CH(CH₃)O—),(—CH(CH₃)CH(CH₃)O—), (—CH₂CH(CH₂CH₃)O—), or a mixture thereof, whereinthe total number of repeat units is in the range of 2 to 100, or anycombination thereof. In another embodiment, at least one hydrophobicorganic group comprises a C₁-C₁₀ alkyl group, a C₁-C₁₀ hydroxyl alkylgroup, a polyether comprising repeat units of (—CH₂CH₂O—),(—CH₂CH(CH₃)O—), (—CH(CH₃)CH(CH₃)O—), (—CH₂CH(CH₂CH₃)O—), or a mixturethereof, wherein the total number of repeat units is in the range of 2to 100, or any combination thereof. In an additional embodiment, atleast one hydrophobic organic group comprises a C₆-C₂₀ aryl group,optionally substituted with alkyl groups. In a further embodiment, thearyl group is a tolyl group.

Further, the poly alpha-1,6-glucan derivatives disclosed here aresubstantially free from hydrophilic group modifications. Herein, thehydrophilic group are typically selected from carboxylic acid,carboxylic acid salt, sulfonic acid derivative, sulfonic acid derivativesalt, sulfuric acid derivative, sulfuric acid derivative salt,thiosulfate, thiosulfate salt, phosphoric acid derivative, phosphoricacid derivative salt, alkyl amine, alkyl substituted ammonium salt,quaternized pyridine salt, quaternized imidazole salt, or anycombination thereof. The hydrophilic group may include a carboxylicacid, an alkyl substituted ammonium salt, a sulfonate, an alkylsulfonate, a sulfate, a thiosulfate, or any combination thereof.

The poly alpha-1,6-glucan derivatives disclosed herein containhydrophobic organic group substituents and are of interest due to theirsolubility characteristics in water, which can be varied by appropriateselection of substituents and the degree of substitution. Compositionscomprising the poly alpha-1,6-glucan derivatives can be useful in a widerange of applications, including laundry and dish applications. Polyalpha-1,6-glucan derivative shaving greater than 0.1 weight percent (wt%) solubility in water can be useful as rheology modifiers, emulsionstabilizers, and dispersing agents in compositions, wherein the productsare in a primarily water-based formulation and optical clarity isdesired. Poly alpha-1,6-glucan derivatives having less than 0.1 wt %solubility in water can be useful as rheology modifiers, emulsionstabilizers, and dispersing agents in laundry and dish applications,wherein the products are typically in formulations which contain organicsolvents to solubilize or disperse the poly alpha-1,6-glucanderivatives. In one embodiment of the composition, the polyalpha-1,6-glucan derivative has a DoS of about 0.20 to about 1.50 and asolubility of 0.1% by weight or higher in deionized water at 25° C. Inanother embodiment of the composition, the poly alpha-1,6-glucanderivative has a DoS of about 0.20 to about 1.50 and a solubility ofless than 0.1% by weight in pH 7 water at 25° C.

Compositions comprising poly alpha-1,6-glucan derivatives can besustainable materials in the above mentioned applications. Furthermore,biodegradable alpha-1,6-glucan derivatives are preferred overnon-biodegradable materials from an environmental footprint perspective.Biodegradability of a material can be evaluated by methods known in theart, for example as disclosed in the Examples section herein below. Inone embodiment, the poly alpha-1,6-glucan derivative has abiodegradability as determined by the OECD 301B Ready BiodegradabilityCO₂ Evolution Test Method of at least 10% on the 90^(th) day testduration. In another embodiment, the poly alpha-1,6-glucan derivativehas a biodegradability as determined by the OECD 301B ReadyBiodegradability Test Method of at least 5%, 10%, 15%, 20%, 25%, 30%,35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%, or any valuebetween 5% and 80%, on the 90^(th) day test duration. In yet anotherembodiment, the poly alpha-1,6-glucan derivative has a biodegradabilityas determined by the OECD 301B Ready Biodegradability CO₂ Evolution TestMethod of at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%,or 60%, or any value between 5% and 60%, on the 60^(th) day testduration.

The poly alpha-1,6-glucan derivatives disclosed herein can be comprisedin a personal care product, pharmaceutical product, household product,or industrial product in an amount that provides a desired degree of oneor more of the following physical properties to the product: thickening,freeze/thaw stability, lubricity, moisture retention and release,texture, consistency, shape retention, emulsification, binding,suspension, dispersion, and gelation, for example. Examples of aconcentration or amount of a poly alpha-1,6-glucan derivative asdisclosed herein in a product, on a weight basis, can be about 0.1-3 wt%, 1-2 wt %, 1.5-2.5 wt %, 2.0 wt %, 0.1-4 wt %, 0.1-5 wt %, or 0.1-10wt %, for example.

The terms “poly alpha-1,6-glucan” and “dextran” are used interchangeablyherein. Dextrans represent a family of complex, branched alpha-glucansgenerally comprising chains of alpha-1,6-linked glucose monomers, withperiodic side chains (branches) linked to the straight chains byalpha-1,3-linkage (Joan et al., Macromolecules 33:5730-5739) and/oralpha-1,2-linkage. Production of dextran for producing a polyalpha-1,6-glucan derivative herein can be done, for example, throughfermentation of sucrose with bacteria (e.g., Leuconostoc orStreptococcus species), where sucrose serves as the source of glucosefor dextran polymerization (Naessens et al., J. Chem. Technol.Biotechnol. 80:845-860; Sarwat et al., Int. J. Biol. Sci. 4:379-386;Onilude et al., Int. Food Res. J. 20:1645-1651). Alternatively, polyalpha-1,6-glucan can be prepared using a glucosyltransferase(dextransucrase) such as (but not limited to) GTF1729, GTF1428, GTF5604,GTF6831, GTF8845, GTF0088, and GTF8117 as described in WO2015/183714 andWO2017/091533, both of which are incorporated herein by reference.

In some embodiments, the poly alpha-1,6-glucan derivative comprises abackbone of glucose monomer units wherein greater than or equal to 40%,45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 90%, 95%, 96%, 97%, 98%, 99%,99.5%, or 100% of the glucose monomer units are linked viaalpha-1,6-glycosidic linkages. The backbone of the poly alpha-1,6-glucanderivative can comprise, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 10%,15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60% glucose monomerunits which are linked via alpha-1,2, alpha-1,3, and/or alpha-1,4glycosidic linkages. In some aspects, the poly alpha-1,6-glucanderivative comprises a backbone that is linear (unbranched).

Dextran “long chains” herein can comprise “substantially (or mostly)alpha-1,6-glucosidic linkages”, meaning that they can have at leastabout 98.0% alpha-1,6-glucosidic linkages in some aspects. Dextranherein can comprise a “branching structure” (branched structure, such asdendritic) in some aspects. It is contemplated that in this structure,long chains branch from other long chains, likely in an iterative manner(e.g., a long chain can be a branch from another long chain, which inturn can itself be a branch from another long chain, and so on). It iscontemplated that long chains in this structure can be “similar inlength”, meaning that the length (DP [degree of polymerization]) of atleast 70% of all the long chains in a branching structure is withinplus/minus 30% of the mean length of all the long chains of thebranching structure.

Dextran in some embodiments can also comprise “short chains” branchingfrom the long chains, typically being one to three glucose monomers inlength, and typically comprising less than about 10% of all the glucosemonomers of a dextran polymer. Such short chains typically comprisealpha-1,2-, alpha-1,3-, and/or alpha-1,4-glucosidic linkages (it isunderstood that there can also be a small percentage of suchnon-alpha-1,6 linkages in long chains in some aspects). In certainembodiments, the poly-1,6-glucan with branching is producedenzymatically according to the procedures in WO2015/183714 andWO2017/091533 (both incorporated herein by reference) where, forexample, alpha-1,2-branching enzymes such as GTFJ18T1 or GTF9905 can beadded during or after the production of the dextran polymer(polysaccharide). In some embodiments, any other enzyme known to producealpha-1,2-branching can be added. Poly alpha-1,6-glucan withalpha-1,3-branching can be prepared as disclosed in Vuillemin et al.(2016, J. Biol Chem. 291:7687-7702) or U.S. Appl. No. 62/871,796, whichare incorporated herein by reference. The degree of branching of polyalpha-1,6-glucan or a poly alpha-1,6-glucan derivative in suchembodiments has less than or equal to 50%, 40%, 30%, 20%, 10%, or 5% (orany integer value between 5% and 50%) of short branching, for examplealpha-1,2-branching or 1,3-branching. In one embodiment, the polyalpha-1,6-glucan or the poly alpha-1,6-glucan derivative has a degree ofalpha-1,2-branching that is less than 50%. In another embodiment, thepoly alpha-1,6-glucan or the poly alpha-1,6-glucan derivative has adegree of alpha-1,2-branching that is at least 5%. In one embodiment, atleast 5% of the backbone glucose monomer units of the polyalpha-1,6-glucan derivative have branches via alpha-1,2- oralpha-1,3-glycosidic linkages. In one embodiment, the polyalpha-1,6-glucan or the poly alpha-1,6-glucan derivative comprises abackbone of glucose monomer units wherein greater than or equal to 40%of the glucose monomer units are linked via alpha-1,6-glycosidiclinkages. In one embodiment, the poly alpha-1,6-glucan derivativecomprises a backbone of glucose monomer units wherein greater than orequal to 40% of the glucose monomer units are linked viaalpha-1,6-glycosidic linkages and at least 5% of the glucose monomerunits have branches via alpha-1,2- or alpha-1,3-glycosidic linkages. Inone embodiment, the poly alpha-1,6-glucan derivative comprises abackbone of glucose monomer units wherein greater than or equal to 40%of the glucose monomer units are linked via alpha-1,6-glycosidiclinkages and at least 5% of the glucose monomer units have branches viaalpha-1,2 linkages. In one embodiment, the poly alpha-1,6-glucanderivative comprises a backbone of glucose monomer units wherein greaterthan or equal to 40% of the glucose monomer units are linked viaalpha-1,6-glycosidic linkages and at least 5% of the glucose monomerunits have branches via alpha-1,3 linkages. In one embodiment, the polyalpha-1,6-glucan or poly alpha-1,6-glucan derivative is linear, orpredominantly linear. In some aspects, about, at least about, or lessthan about, 1%, 2%, 3%, 4%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%,55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90% of the backbone glucosemonomer units of a poly alpha-1,6-glucan or derivative thereof aspresently disclosed can have branches via alpha-1,2 and/or alpha-1,3glycosidic linkages. In some aspects, about, at least about, or lessthan about, 1%, 2%, 2.5%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, or 45%of all the glycosidic linkages of an alpha-1,2- and/oralpha-1,3-branched poly alpha-1,6-glucan or derivative thereof aspresently disclosed are alpha-1,2 and/or alpha-1,3 glycosidic linkages.The amount of alpha-1,2-branching or alpha-1,3-branching can bedetermined by NMR methods, as disclosed in the Examples.

The poly alpha-1,6-glucan and poly alpha-1,6-glucan derivativesdisclosed herein can have a number-average degree of polymerization(DPn) or weight-average degree of polymerization (DPw) in the range of 5to 4000. In some embodiments, the DPn or DPw can be in the range of 5 to100, 5 to 500, 5 to 1000, 5 to 1500, 5 to 2000, 5 to 2500, 5 to 3000, or5 to 4000. In some embodiments, the DPn or DPw can be in the range of 50to 500, 50 to 1000, 50 to 1500, 50 to 2000, 50 to 3000, or 50 to 4000.In some embodiments, the DPn or DPw can be in the range of 400 to 4000,400 to 3000, 400 to 2000, or 400 to 1000. In some embodiments, the DPnor DPw can be about, at least about, or less than about, 5, 10, 25, 50,100, 250, 500, 1000, 1500, 2000, 2500, 3000, 4000, 5000, 6000, 5-100,5-250, 5-500, 5-1000, 5-1500, 5-2000, 5-2500, 5-3000, 5-4000, 5-5000,5-6000, 10-100, 10-250, 10-500, 10-1000, 10-1500, 10-2000, 10-2500,10-3000, 10-4000, 10-5000, 10-6000, 25-100, 25-250, 25-500, 25-1000,25-1500, 25-2000, 25-2500, 25-3000, 25-4000, 25-5000, 25-6000, 50-100,50-250, 50-500, 50-1000, 50-1500, 50-2000, 50-2500, 50-3000, 50-4000,50-5000, 50-6000, 100-100, 100-250, 100-500, 100-1000, 100-1500,100-2000, 100-2500, 100-3000, 100-4000, 100-5000, or 100-6000.

The poly alpha-1,6-glucan derivative comprises:

-   -   (i) a poly alpha-1,6-glucan backbone of glucose monomer units,        wherein greater than or equal to 40% of the glucose monomer        units are linked via alpha-1,6 glycosidic linkages, and        optionally at least 5% of the backbone glucose monomer units        have branches via alpha-1,2 and/or alpha-1,3 glycosidic        linkages; and    -   (ii) at least one hydrophobic organic group linked to the poly        alpha-1,6-glucan backbone through an ether (—O—) linkage moiety;        wherein, the poly alpha-1,6-glucan backbone has a weight average        degree of polymerization of at least 5;        wherein, the poly alpha-1,6-glucan derivative has a degree of        substitution of ether linkage moiety of from 0.20 to 1.00; and        wherein, the poly alpha-1,6-glucan derivative is substantially        free from hydrophilic substitution.

The poly alpha-1,6-glucan derivative comprises poly alpha-1,6-glucansubstituted with at least one hydrophobic organic group on thepolysaccharide backbone and/or on one or more of the optional branches.When substitution occurs on a glucose monomer contained in the backbone,the polysaccharide is derivatized at the 2, 3, and/or 4 glucose carbonposition(s) with a hydrophobic organic group as defined herein which islinked to the polysaccharide through a linkage moiety. When substitutionoccurs on a glucose monomer contained in a branch, the polysaccharide isderivatized at the 2, 3, 4, and/or 6 glucose carbon position(s) with ahydrophobic organic group as defined herein which is linked to thepolysaccharide through a linkage moiety. The hydrophobic organic groupsare independently linked to the poly alpha-1,6-glucan through an —O—(ether) linkage moiety in place of the hydroxyl group originally presentin the underivatized (unsubstituted) poly alpha-1,6-glucan.

When the linkage moiety is —O—, a poly alpha-1,6-glucan derivative istermed a glucan “ether” compound herein by virtue of comprising thesubstructure —C_(G)—O—C_(R)—, wherein “—C_(G)—” represents a carbon of aglucose monomer unit of a poly alpha-1,6-glucan ether compound, andwherein “—C_(R)—” is comprised in the hydrophobic organic group. In oneembodiment, the linkage moiety is —O— and the poly alpha-1,6-glucanderivative comprises a poly alpha-1,6-glucan ether compound. A polyalpha-1,6-glucan monoether compound contains the linkage moiety —O— andone type of hydrophobic organic group. A poly alpha-1,6-glucan mixedether compound contains the linkage moiety —O— and two or more types ofa hydrophobic organic group.

In one embodiment, at least one linkage moiety is —O— and at least onelinkage moiety is —OSO₂—, and the poly alpha-1,6-glucan derivativecomprises both ether and sulfonyl substituents. In another embodiment,at least one linkage moiety is —O— and at least one linkage moiety is—OCOO—, and the poly alpha-1,6-glucan derivative comprises both etherand carbonate substituents. In another embodiment, at least one linkagemoiety is —O— and at least one linkage moiety is —OCONH—, and the polyalpha-1,6-glucan derivative comprises both ether and carbamatesubstituents.

Compositions disclosed herein can comprise, or consist essentially of,one or more poly alpha-1,6-glucan derivatives as disclosed herein. Inone embodiment, a composition can comprise one poly alpha-1,6-glucanderivative. In another embodiment, a composition may comprise two ormore poly alpha-1,6-glucan derivatives wherein the linkage moieties arethe same and the hydrophobic organic groups are different, or two ormore derivatives wherein the linkage moieties (when a combination ofether and a second linkage group) are different and the hydrophobicorganic groups are the same. A composition may also comprise two or morederivatives wherein both the linkage moieties and the hydrophobicorganic groups are different.

The term “degree of substitution” (DoS) as used herein refers to theaverage number of hydroxyl groups substituted in each monomeric unit(glucose) of a poly alpha-1,6-glucan derivative, which includes themonomeric units within the backbone and within any alpha-1,2 oralpha-1,3 branches which may be present. Since there are at most threehydroxyl groups in a glucose monomeric unit in a poly alpha-1,6-glucanpolymer, the overall degree of substitution of a poly alpha-1,6-glucanderivative herein can be no higher than 3.00. It would be understood bythose skilled in the art that, since a poly alpha-1,6-glucan derivativeas disclosed herein can have a degree of substitution between about 0.01to about 3.00, the substituents on the polysaccharide cannot only behydroxyl. The degree of substitution of a poly alpha-1,6-glucanderivative can be stated with reference to a specific substituent orwith reference to the overall degree of substitution, that is, the sumof the DoS of each different substituent for a glucan derivative asdefined herein. As used herein, when the degree of substitution is notstated with reference to a specific substituent or substituent type, theoverall degree of substitution of the poly alpha-1,6-glucan derivativeis meant. The target DoS can be chosen to provide the desired solubilityand performance of a composition comprising a poly alpha-1,6-glucanderivative in the specific application of interest.

The poly alpha-1,6-glucan derivatives disclosed herein have a DoS in therange of about 0.0.20 to about 3.00, for example of about 0.20 to about2.50, or for example of about 0.0.20 to about 2.00, or for example ofabout 0.20 to about 1.50, or for example of about 0.20 to 1.40, or forexample 0.20 to 1.30, or for example 0.20 to 1.20, or for example 0.20to 1.00, about 0.20 to about 0.80, or for example of about 0.20 to about0.60, or for example of about 0.20 to about 0.40. The degree ofsubstitution of a poly alpha-1,6-glucan derivative can be stated withreference to a specific substituent or with reference to the overalldegree of substitution, that is, the sum of the DoS of each differentsubstituent type for a glucan derivative as defined herein. As usedherein, when the degree of substitution is not stated with reference toa specific substituent type, the overall degree of substitution of thepoly alpha-1,6-glucan derivative is meant.

The poly alpha-1,6-glucan derivatives disclosed herein have a DoS ofether linkage moiety of from 0.20 to 1.00, or in the range of about 0.20to about 1.00, for example of about 0.20 to about 0.80, or for exampleof about 0.20 to about 0.60, or for example of about 0.20 to about 0.40.

In one embodiment of a poly alpha-1,6-glucan derivative disclosedherein, at least one hydrophobic organic group is selected from: a C₁ toC₁₈ alkyl group, a hydroxy alkyl group, a C₂ to C₁₈ alkenyl group, a C₂to C₁₈ alkynyl group, a benzyl group, a C₆ to C₂₀ aryl group, apolyether comprising repeat units of (—CH₂CH₂O—), (—CH₂CH(CH₃)O—),(—CH(CH₃)CH(CH₃)O—), (—CH₂CH(CH₂CH₃)O—), or a mixture thereof, whereinthe total number of repeat units is in the range of 2 to 100, or anycombination thereof.

The term “alkyl group”, as used herein, refers to linear, branched, orcyclic (“cycloalkyl” or “cycloaliphatic”) hydrocarbon groups containingno unsaturation. The alkyl group can be substituted, for example withanother alkyl group or with at least one hydroxyalkyl group or dihydroxyalkyl group. In one embodiment, the hydrophobic organic group is a C₁ toC₁₈ alkyl group, for example a C₄ to C₁₈ alkyl group, or for example aC₁ to C₁₀ alkyl group. The alkyl group may be, for example, a methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecanyl, tetradecanyl, pentadecanyl, hexadecanyl,heptadecanyl, or octadecanyl group. One or more carbons of an alkylgroup can be substituted with another alkyl group, making the alkylgroup branched. Examples of branched chain isomers of linear alkylgroups include isopropyl, iso-butyl, tert-butyl, sec-butyl, isopentyl,neopentyl, isohexyl, neohexyl, 2-ethylhexyl, 2-propylheptyl, andisooctyl. In one embodiment, the hydrophobic organic group is a methylgroup. In one embodiment, the hydrophobic organic group is an ethylgroup. In one embodiment, the hydrophobic organic group is a propylgroup.

One or more carbons of an alkyl group can be substituted with at leastone hydroxyalkyl group. Suitable hydroxyalkyl groups are hydroxymethyl(—CH₂OH), hydroxyethyl (e.g., —CH₂CH₂OH, —CH(OH)CH₃), hydroxypropyl(e.g., —CH₂CH₂CH₂OH, —CH₂CH(OH)CH₃, —CH(OH)CH₂CH₃), hydroxybutyl, andhydroxypentyl groups. Other examples include dihydroxy alkyl groups(diols) such as dihydroxymethyl, dihydroxyethyl, dihydroxypropyl,dihydroxybutyl and dihydroxypentyl. In another embodiment, the alkylgroup is a cycloalkyl group, and the cycloalkyl group may be, forexample, a cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,or cyclodecyl group. In one embodiment, the cycloalkyl group is a C₅ toC₁₀ cycloalkyl group. In one embodiment, the hydrophobic organic groupis a hydroxy alkyl group.

A substitution on an alkyl group in certain embodiments may be bonded tothe terminal carbon atom of the alkyl group, where the terminal carbongroup is opposite the carbon atom that is linked to the ether, sulfonyl,carbonate, or carbamate moiety, which in turn is linked to an oxygen ofthe glucan polymer. An example of this terminal substitution is in thehydroxypropyl group —CH₂CH₂CH₂OH. Alternatively, a substitution may beon an internal carbon atom of an alkyl group. An example on an internalsubstitution is in the hydroxypropyl group —CH₂CH(OH)CH₃.

In another embodiment, an alkyl group can contain one or moreheteroatoms such as oxygen, sulfur, and/or nitrogen within thehydrocarbon chain. In another embodiment, an alkyl group can contain oneor more heteroatoms such as oxygen and/or sulfur within the hydrocarbonchain. Examples include alkyl groups containing an alkyl glycerolalkoxylate moiety (-alkylene-OCH₂CH(OH)CH₂OH), a moiety derived fromring-opening of 2-ethylhexyl glycidyl ether, and a tetrahydropyranylgroup, for example as derived from dihydropyran. Derivatives preparedwith dihydropyran or alternatively dihydrofuran would afford acetallinkages with the polyglucan backbone. The acetal linkage is representedby R₂C(OR′)₂) where R′ are joined together in the cyclic ring of thedihydropyran or dihydrofuran.

In another embodiment, the hydrophobic organic group is a C₂ to C₁₈alkenyl group, and the alkenyl group may be linear, branched, or cyclic.As used herein, the term “alkenyl group” refers to hydrocarbon groupscontaining at least one carbon-carbon double bond. Examples of alkenylgroups include ethenyl, propenyl, butenyl, pentenyl, hexenyl,cyclohexyl, and allyl groups. In other embodiments, one or more carbonsof the alkenyl group can have substitution(s) with an alkyl group, orwith a hydroxyalkyl or dihydroxy alkyl group. Examples of suchsubstituent alkyl groups include methyl, ethyl, and propyl groups. Inone embodiment, the alkenyl group is a C₄ to C₁₈ alkene group.

Optionally, an alkenyl group can contain one or more heteroatoms such asoxygen, sulfur, and/or nitrogen within the hydrocarbon chain, forexample an alkenyl group can contain a moiety derived from ring-openingof an allyl glycidyl ether.

In another embodiment, the hydrophobic organic group is a C₂ to C₁₈alkynyl group. As used herein, the term “alkynyl” refers to linear andbranched hydrocarbon groups containing at least one carbon-carbon triplebond. The alkynyl group may be, for example, propyne, butyne, pentyne,or hexyne. The alkynyl group may be substituted, for example with alkyl,hydroxyalkyl, or dihydroxy alkyl groups. Optionally, an alkynyl groupcan contain one or more heteroatoms such as oxygen, sulfur, and/ornitrogen within the hydrocarbon chain.

In another embodiment, the hydrophobic organic group is a polyethercomprising repeat units of (—CH₂CH₂O—), (—CH₂CH(CH₃)O—),(—CH(CH₃)CH(CH₃)O—), (—CH₂CH(CH₂CH₃)O—), or a mixture thereof, whereinthe total number of repeat units is in the range of 2 to 100. In oneembodiment, the hydrophobic organic group is a polyether groupcomprising (—CH₂CH₂O—)₄₋₁₀₀. In another embodiment, the hydrophobicorganic group is a polyether group comprising (—CH₂CH(CH₃)O—)₄₀₋₁₀₀. Inanother embodiment, the hydrophobic organic group is a polyether groupcomprising (—CH₂CH(CH₂CH₃)O—)₂₋₁₀₀. In another embodiment, thehydrophobic organic group is a polyether group comprising(—CH(CH₃CH(CH₃)O—)₂₋₁₀₀. As used herein, the subscript designating arange of values will be used to designate the potential number of repeatunits, for example, (CH₂CH₂O)₂₋₁₀₀ means a polyether group containing inthe range of from 2 to 100 repeat units. In some aspects, a polyethergroup herein can be capped such as with a methoxy, ethoxy, or propoxygroup.

In another embodiment, the hydrophobic organic group is an aryl group.As used herein, the term “aryl” means an aromatic/carbocyclic grouphaving a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), ormultiple condensed rings in which at least one is aromatic, (e.g.,1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl), which isoptionally mono-, di-, or trisubstituted with alkyl groups, such as amethyl, ethyl, or propyl group. In one embodiment, the aryl group is aC₆ to C₂₀ aryl group. In another embodiment, the aryl group is a methylsubstituted aryl group, for example a tolyl (—C₆H₄CH₃) or xylyl[—C₆H₃(CH₃)₂] group. In a further embodiment, the tolyl group is ap-tolyl group. In yet another embodiment, the aryl group is a benzylgroup (—CH₂—C₆H₅). The benzyl group can optionally be furthersubstituted with one or more of a halogen, a cyano, an ester, an amide,an ether group, a C₁ to C₆ alkyl group, an aryl group, a C₂ to C₆ alkenegroup, a C₂ to C₆ alkyne group, or any combination thereof. In anadditional embodiment, the aryl group is a phenyl group.

In one embodiment, the poly alpha-1,6-glucan derivative has a DoS ofether linkage moiety about 0.20 to about 1.00, at least one linkagemoiety is —O—, and at least one hydrophobic organic group is a methyl,ethyl, phenyl, benzyl, or p-tolyl group. In another embodiment, the polyalpha-1,6-glucan derivative has a DoS of ether linkage moiety about 0.20to about 0.80, at least one linkage moiety is —O—, and at least onehydrophobic organic group is a methyl, ethyl, phenyl, benzyl, or p-tolylgroup. In a further embodiment, the poly alpha-1,6-glucan derivative hasa DoS of ether linkage moiety about 0.20 to about 0.60, at least onelinkage moiety is —O—, and at least one hydrophobic organic group is amethyl, ethyl, phenyl, benzyl, or p-tolyl group. In yet anotherembodiment, the poly alpha-1,6-glucan derivative has a DoS of etherlinkage moiety about 0.20 to about 0.40, at least one linkage moiety is—O—, and at least one hydrophobic organic group is a methyl, ethyl,phenyl, benzyl, or p-tolyl group.

In one embodiment, the poly alpha-1,6-glucan derivative has a DoS ofabout 0.20 to about 1.00, at least one linkage moiety is —O— and atleast one linkage moiety is —OSO₂—, and at least one hydrophobic organicgroup is a methyl, ethyl, phenyl, benzyl, or p-tolyl group. In anotherembodiment, the poly alpha-1,6-glucan derivative has a DoS of about 0.20to about 1.00, at least one linkage moiety is —O— and at least onelinkage moiety is —OSO₂—, and at least one hydrophobic organic group isa methyl, ethyl, phenyl, benzyl, or p-tolyl group. In a furtherembodiment, the poly alpha-1,6-glucan derivative has a DoS of about 0.20to about 0.60, at least one linkage moiety is —O— and at least onelinkage moiety is —OSO₂—, and at least one hydrophobic organic group isa methyl, ethyl, phenyl, benzyl, or p-tolyl group. In yet anotherembodiment, the poly alpha-1,6-glucan derivative has a DoS of about 0.20to about 1.00, at least one linkage moiety is —O— and at least onelinkage moiety is —OSO₂—, and at least one hydrophobic organic group isa methyl, ethyl, phenyl, benzyl, or p-tolyl group.

In one embodiment of a poly alpha-1,6-glucan derivative, the linkagemoiety is —O—, the DoS of ether linkage moiety is from 0.20 to 1.00, andat least one hydrophobic organic group comprises a C₁ to C₁₈ alkylgroup, a hydroxy alkyl group, a C₂ to C₁₈ alkenyl group, a C₂ to C₁₈alkynyl group, a benzyl group, a C₆ to C₂₀ aryl group, a polyethercomprising repeat units of (—CH₂CH₂O—) (—CH₂CH(CH₃)O—),(—CH(CH₃)CH(CH₃)O—), (—CH₂CH(CH₂CH₃)O—), or a mixture thereof, whereinthe total number of repeat units is in the range of from 2 to 100, orany combination thereof. In another embodiment, the linkage moiety is—O—, the DoS is from 0.20 to 1.00, and at least one hydrophobic organicgroup comprises a C₁-C₁₀ alkyl group, a C₁-C₁₀ hydroxyl alkyl group, apolyether comprising repeat units of (—CH₂CH₂O—), (—CH₂CH(CH₃)O—),(—CH(CH₃)CH(CH₃)O—), (—CH₂CH(CH₂CH₃)O—), or a mixture thereof, whereinthe total number of repeat units is in the range of 2 to 100, or anycombination thereof. In an additional embodiment, the linkage moiety is—O—, the DoS of ether linkage moiety is from 0.20 to 1.00, and at leastone hydrophobic organic group comprises a benzyl group or a benzyl groupsubstituted with one or more of a halogen, a cyano, an ester, an amide,an ether group, a C₁ to C₆ alkyl group, an aryl group, a C₂ to C₆ alkenegroup, a C₂ to C₆ alkyne group, or any combination thereof. In a furtherembodiment, the linkage moiety is —O—, the DoS of ether linkage moietyis from 0.20 to 1.00, and at least one hydrophobic organic groupcomprises a C₁-C₁₀ alkyl group, C₁-C₁₀ hydroxyl alkyl group, a polyethercomprising repeat units of (—CH₂CH₂O—), (—CH₂CH(CH₃)O—),(—CH(CH₃)CH(CH₃)O—), (—CH₂CH(CH₂CH₃)O—), or a mixture thereof, whereinthe total number of repeat units is in the range of from 2 to 100, abenzyl group, or any combination thereof. In yet another embodiment, thelinkage moiety is —O—, the DoS of ether linkage moiety is from 0.20 to1.00, and at least one hydrophobic organic group comprises a C₆-C₂₀ arylgroup, optionally substituted with alkyl groups.

Poly alpha-1,6-glucan may be derivatized to an ether compound bycontacting the polysaccharide with at least one etherification agentcomprising the desired hydrophobic organic group under alkalineconditions. This step can be performed, for example, by first preparingalkaline conditions by contacting the polysaccharide with a solvent andone or more alkali hydroxides to provide a solution or mixture. Thealkaline conditions of the reaction can thus comprise an alkalihydroxide solution. The pH of the alkaline conditions can be about, orat least about, 11.0, 11.2, 11.4, 11.6, 11.8, 12.0, 12.2, 12.4, 12.6,12.8, or 13.0.

Useful etherification agents may include, for example, dialkyl sulfates,dialkyl carbonates, alkyl halides (e.g., alkyl chloride), iodoalkanes,alkyl triflates (alkyl trifluoromethanesulfonates), alkylfluorosulfonates, 1,2-epoxyalkyls, and epoxides. Thus, examples ofetherification agents for producing methyl poly alpha-1,6-glucan ethersinclude dimethyl sulfate, dimethyl carbonate, methyl chloride,iodomethane, methyl triflate, methyl fluorosulfonate. Examples ofetherification agents for producing ethyl poly alpha-1,6-glucan ethersinclude diethyl sulfate, diethyl carbonate, ethyl chloride, iodoethane,ethyl triflate and ethyl fluorosulfonate. Examples of etherificationagents for producing propyl poly alpha-1,6-glucan ethers includedipropyl sulfate, dipropyl carbonate, propyl chloride, iodopropane,propyl triflate and propyl fluorosulfonate. Examples of etherificationagents for producing butyl poly alpha-1,6-glucan ethers include dibutylsulfate, dibutyl carbonate, butyl chloride, iodobutane, butyl triflate,and 1,2-epoxybutane. Examples of etherification agents for producingbenzyl poly alpha-1,6-glucan ethers include benzyl chloride and benzylbromide.

Poly alpha-1,6-glucan ethers wherein the hydrophobic organic group is apolyether comprising repeat units of (—CH₂CH₂O—), (—CH₂CH(CH₃)O—),(—CH(CH₃)CH(CH₃)O—), (—CH₂CH(CH₂CH₃)O—), or a mixture thereof, may alsobe obtained by contacting the glucan with an epoxide, for example,ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide,or a mixture thereof, in the presence of a base. The hydroxyl group mayundergo further reaction with an epoxide, producing a polyether havingtwo or more ether repeat units. Depending on the molar amounts of theepoxide and the poly alpha-1,6-glucan, one or more of the hydroxylgroups of the glucan can be monoalkoxylated or polyalkoxylated.

Etherification agents suitable for preparing a dihydroxyalkyl polyalpha-1,6-glucan ether compound include dihydroxyalkyl halides (e.g.,dihydroxyalkyl chloride) such as dihydroxyethyl halide, dihydroxypropylhalide (e.g., 2,3-dihydroxypropyl chloride [i.e.,3-chloro-1,2-propanediol]), or dihydroxybutyl halide, for example.2,3-Dihydroxypropyl chloride can be used to prepare dihydroxypropyl polyalpha-1,6-glucan, for example.

When producing a poly alpha-1,6-glucan ether compound with two or moredifferent hydrophobic organic groups, two or more differentetherification agents would be used, accordingly. For example, both analkylene oxide and an alkyl chloride could be used as etherificationagents to produce an alkyl hydroxyalkyl poly alpha-1,6-glucan ether. Anyof the etherification agents disclosed herein may therefore be combinedto produce poly glucan ether compounds with two or more differenthydrophobic organic groups. Such two or more etherification agents maybe used in the reaction at the same time or may be used sequentially inthe reaction. When used sequentially, any of the temperature-treatment(e.g., heating) steps disclosed below may optionally be used betweeneach addition. One may choose sequential introduction of etherificationagents in order to control the desired DoS of each hydrophobic organicgroup. In general, a particular etherification agent would be used firstif the hydrophobic organic group it forms in the ether product isdesired at a higher DoS compared to the DoS of another hydrophobicorganic group to be added.

The amount of etherification agent to be contacted with polyalpha-1,6-glucan in a reaction under alkaline conditions can bedetermined based on the degree of substitution required in the ethercompound being produced. The amount of ether substitution groups on eachmonomeric unit in poly alpha-1,6-glucan ether compounds produced hereincan be determined using nuclear magnetic resonance (NMR) spectroscopy.The molar substitution (MS) value for poly alpha-1,6-glucan has no upperlimit. In general, an etherification agent can be used in a quantity ofat least about 0.05 mole per mole of poly glucan. There is no upperlimit to the quantity of etherification agent that can be used.

Reactions for producing poly alpha-1,6-glucan ether compounds herein canoptionally be carried out in a pressure vessel such as a Parr reactor,an autoclave, a shaker tube or any other pressure vessel well known inthe art. A shaker tube may be used to perform the reaction in certainembodiments.

A reaction herein can optionally be heated following the step ofcontacting the poly glucan with an etherification agent under alkalineconditions. The reaction temperatures and time of applying suchtemperatures can be varied within wide limits. For example, a reactioncan optionally be maintained at ambient temperature for up to 14 days.Alternatively, a reaction can be heated, with or without reflux, betweenabout 25° C. to about 200° C. (or any integer between 25 and 200° C.).Reaction time can be varied correspondingly: more time at a lowtemperature and less time at a high temperature.

Optionally, a reaction herein can be maintained under an inert gas, withor without heating. As used herein, the term “inert gas” refers to a gaswhich does not undergo chemical reactions under a set of givenconditions, such as those disclosed for preparing a reaction herein.

All of the components of the reactions disclosed herein can be mixedtogether at the same time and brought to the desired reactiontemperature, whereupon the temperature is maintained with or withoutstirring until the desired poly glucan ether compound is formed.Alternatively, the mixed components can be left at ambient temperatureas described above.

Following etherification, the pH of a reaction can be neutralized.Neutralization of a reaction can be performed using one or more acids.The term “neutral pH” as used herein, refers to a pH that is neithersubstantially acidic or basic (e.g., a pH of about 6-8, or about 6.0,6.2, 6.4, 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8, or 8.0). Various acids thatcan be used for this purpose include, but are not limited to, sulfuric,acetic, hydrochloric, nitric, any mineral (inorganic) acid, any organicacid, or any combination of these acids.

A poly alpha-1,6-glucan derivative produced in a reaction as disclosedherein can optionally be washed one or more times with a liquid thatdoes not readily dissolve the compound. For example, a polyalpha-1,6-glucan can be washed with water, alcohol, acetone, aromatics,or any combination of these, depending on the solubility of the ethercompound therein (where lack of solubility is desirable for washing). Ingeneral, a solvent comprising an organic solvent such as alcohol ispreferred for the washing. A poly glucan product can be washed one ormore times with an aqueous solution containing methanol or ethanol, forexample. For example, 70-95 wt % ethanol can be used to wash theproduct. A poly glucan product can be washed with a methanol:acetone(e.g., 60:40) solution in another embodiment. Hot water (about 95-100°C.) can be used in certain embodiments, such as for washing alkyl polyalpha-1,6-glucan ethers (e.g., ethyl poly alpha-1,6-glucan) and alkylhydroxyalkyl poly alpha-1,6-glucan ethers (e.g., ethyl hydroxyethyl polyalpha-1,6-glucan).

The poly alpha-1,6-glucan can also be modified with one or more benzylgroups. The poly glucan can be benzylated by deprotonating one or moreof the hydroxyl groups using a base, for example, sodium hydroxide,potassium hydroxide, sodium alkoxide, potassium alkoxide, sodium hydridefollowed by treatment with a benzylating agent, for example, a benzylhalide. The benzyl group of the benzylating agent can optionallysubstituted by one or more of halogen, a cyano, an ester, an amide, anether group, a C₁ to C₆ alkyl group, an aryl group, a C₂ to C₆ alkenegroup, a C₂ to C₆ alkyne group, or any combination thereof. In someembodiments, the benzylating agent can be as represented by thefollowing structure:

wherein LG is a leaving group, for example, chloride, bromide, iodide;R³ is halogen, cyano, ester, amide, ether, C₁ to C₆ alkyl, aryl, C₂ toC₆ alkene, C₂ to C₆ alkyne; and n is 1, 2, 3, 4 or 5. Halogen can befluoride, chloride, bromide or iodide. The ester can be benzyl-C(O)O—R¹,or the ester can be benzyl-OC(O)—R¹, wherein the R¹ group is a C₁ to C₆alkyl or an aryl group. The ether can be a C₁ to C₆ alkyl ether or anaryl ether. The amide can be benzyl-C(O)N(R²)₂ or benzyl-N(R²)(O)C—,wherein each R² is independently hydrogen or C₁ to C₆ alkyl. In each ofthe above examples, the term ‘benzyl’ refers to the benzylating agent.

Deprotonation can take place in the presence of a base and an aqueoussolvent, a base and an organic solvent, or a base and a mixture of anaqueous and organic solvent. Suitable organic solvents can include, forexample, dimethyl sulfoxide, dimethyl acetamide, dimethyl formamide,pyridine, 1-methyl-2-pyrrolidinone or any combination thereof. In someembodiments, the poly glucan can be added to a mixture of the base andthe solvent. Optionally, the mixture can be heated. The benzylatingagent, for example, benzyl chloride, can then be added. In an aqueoussystem, as the degree of benzylation increases, the benzyl poly glucanprecipitates from the solution, and can be removed by filtration. Byutilizing organic solvents, or varying the temperature or concentration,the degree of substitution can be increased above 0.40. The benzyl polyglucan can be isolated using known techniques.

Any of the above substitution reactions can be repeated using a polyalpha-1,6-glucan as the starting material for further modification. Thisapproach may be suitable for increasing the DoS of a hydrophobic organicgroup, and/or adding one or more different hydrophobic organic groups ora sulfonyl group to the ether compound. For example, a benzyl polyalpha-1,6-glucan ether product can be used as a substrate for furthermodification with carboxymethyl groups. A poly alpha-1,6-glucan methylether can be used as a substrate for further modification with a benzylether group.

Depending upon the desired application, compositions comprising a polyalpha-1,6-glucan derivative as disclosed herein can be formulated, forexample, blended, mixed, or incorporated into, with one or more othermaterials and/or active ingredients suitable for use in variouscompositions, for example compositions for use in laundry care or dishcare product. The term “compositions comprising a poly alpha-1,6-glucanderivative” in this context may include, for example, aqueousformulations, rheology modifying compositions, fabric treatment/carecompositions, laundry care formulations/compositions, fabric softenersand dish care compositions each comprising a poly alpha-1,6-glucanderivative as disclosed herein.

As used herein, the term “effective amount” refers to the amount of thesubstance used or administered that is suitable to achieve the desiredeffect. The effective amount of material may vary depending upon theapplication. One of skill in the art will typically be able to determinean effective amount for a particular application or subject without undoexperimentation.

The term “resistance to enzymatic hydrolysis” refers to the relativestability of the poly alpha-1,6-glucan derivative to enzymatichydrolysis. Having a resistance to hydrolysis is important for the useof these materials in applications wherein enzymes are present, such asin detergent, fabric care, and/or laundry care applications. In someembodiments, the polysaccharide derivative is resistant to cellulases.In other embodiments, the polysaccharide derivative is resistant toproteases. In still further embodiments, the polysaccharide derivativeis resistant to amylases. In yet other embodiments, the polysaccharidederivative is resistant to lipase. In yet other embodiments, thepolysaccharide derivative is resistant to mannanases. In otherembodiments, the polysaccharide derivative is resistant to multipleclasses of enzymes, for example, two or more cellulases, proteases,amylases, lipases, mannanases, or combinations thereof. Resistance toany particular enzyme will be defined as having at least 10, 20, 30, 40,50, 60, 70, 80, 90, 95 or 100% of the materials remaining aftertreatment with the respective enzyme. The percentage remaining may bedetermined by measuring the supernatant after enzyme treatment usingSEC-HPLC. The assay to measure enzyme resistance can be determined usingthe following procedure: A sample of the poly alpha-1,6-glucanderivative is added to water in a vial and mixed using a PTFE magneticstir bar to create a 1 percent by weight aqueous solution. The aqueousmixture is produced at pH 7.0 and 20° C. After the poly alpha-1,6-glucanderivative thereof has completely dissolved, 1.0 milliliter (mL) (1percent by weight of the enzyme formulation) of cellulase (PURADEX®EGL), amylase (PURASTAR® ST L) protease (SAVINASE© 16.0 L), or lipase(Lipex® 100 L) is added and mixed for 72 hours (hrs) at 20° C. After 72hrs of stirring, the reaction mixture is heated to 70° C. for 10 minutesto inactivate the added enzyme, and the resulting mixture is cooled toroom temperature and centrifuged to remove any precipitate. Thesupernatant is analyzed by SEC-HPLC for recovered poly alpha-1,6-glucanderivative and compared to a control where no enzyme was added to thereaction mixture. Percent changes in area counts for the respective polyalpha-1,6-glucan derivative thereof may be used to test the relativeresistance of the materials to the respective enzyme treatment. Percentchanges in area versus the total will be used to assess the relativeamount of materials remaining after treatment with a particular enzyme.Materials having a percent recovery of at least 10%, preferably at least50, 60, 70, 80, 90, 95 or 100% will be considered “resistant” to therespective enzyme treatment.

The phrase “aqueous composition” herein refers to a solution or mixturein which the solvent is at least about 1% by weight of water and whichcomprises the poly alpha-1,6-glucan derivative.

The terms “hydrocolloid” and “hydrogel” are used interchangeably herein.A hydrocolloid refers to a colloid system in which water is thedispersion medium. A “colloid” herein refers to a substance that ismicroscopically dispersed throughout another substance. Therefore, ahydrocolloid herein can also refer to a dispersion, emulsion, mixture,or solution of the poly alpha-1,6-glucan derivative in water or aqueoussolution.

The term “aqueous solution” herein refers to a solution in which thesolvent is water. The poly alpha-1,6-glucan derivative can be dispersed,mixed, and/or dissolved in an aqueous solution. An aqueous solution canserve as the dispersion medium of a hydrocolloid herein.

The terms “dispersant” and “dispersion agent” are used interchangeablyherein to refer to a material that promotes the formation andstabilization of a dispersion of one substance in another. A“dispersion” herein refers to an aqueous composition comprising one ormore particles, for example, any ingredient of a household product thatare scattered, or uniformly distributed, throughout the aqueouscomposition. It is believed that the poly alpha-1,6-glucan derivativecan act as dispersants in aqueous compositions disclosed herein.

The term “viscosity” as used herein refers to the measure of the extentto which a fluid or an aqueous composition such as a hydrocolloidresists a force tending to cause it to flow. Various units of viscositythat can be used herein include centipoise (cps) and Pascal-second(Pa·s). A centipoise is one one-hundredth of a poise; one poise is equalto 0.100 kg·m⁻¹·s⁻¹. Thus, the terms “viscosity modifier” and“viscosity-modifying agent” as used herein refer to anything that canalter/modify the viscosity of a fluid or aqueous composition.

The terms “fabric”, “textile”, and“cloth” are used interchangeablyhereinto refer to a woven or non-woven material having a network ofnatural and/or artificial fibers. Such fibers can be thread or yarn, forexample.

A “fabric care composition” herein is any composition suitable fortreating fabric in some manner. Suitable examples of such a compositioninclude non-laundering fiber treatments (for desizing, scouring,mercerizing, bleaching, coloration, dying, printing, bio-polishing,anti-microbial treatments, anti-wrinkle treatments, stain resistancetreatments, etc.), laundry care compositions (e.g., laundry caredetergents), and fabric softeners.

The terms “detergent composition”, “heavy duty detergent” and“all-purpose detergent” are used interchangeably herein to refer to acomposition useful for regular washing of a substrate, for example,dishware, cutlery, vehicles, fabrics, carpets, apparel, white andcolored textiles at any temperature. Detergent compositions for treatingof fabrics, hard surfaces and any other surfaces in the area of fabricand home care, include: laundry detergents, fabric conditioners(including softeners), laundry and rinse additives and carecompositions, fabric freshening compositions, laundry prewash, laundrypretreat, hard surface treatment compositions, car care compositions,dishwashing compositions (including hand dishwashing and automaticdishwashing products), air care products, detergent contained on or in aporous substrate or nonwoven sheet, and other cleaner products forconsumer or institutional use.

The terms “cellulase” and “cellulase enzyme” are used interchangeablyherein to refer to an enzyme that hydrolyzes β-1,4-D-glucosidic linkagesin cellulose, thereby partially or completely degrading cellulose.Cellulase can alternatively be referred to as “β-1,4-glucanase”, forexample, and can have endocellulase activity (EC 3.2.1.4), exocellulaseactivity (EC 3.2.1.91), or cellobiase activity (EC 3.2.1.21). Acellulase in certain embodiments herein can also hydrolyzeβ-1,4-D-glucosidic linkages in cellulose ether derivatives such ascarboxymethyl cellulose. “Cellulose” refers to an insolublepolysaccharide having a linear chain of β-1,4-linked D-glucose monomericunits.

As used herein, the term “fabric hand” or “handle” is meant people'stactile sensory response towards fabric which may be physical,physiological, psychological, social or any combination thereof. In someembodiments, the fabric hand may be measured using a PHABROMETER® System(available from Nu Cybertek, Inc. Davis, Calif.) for measuring therelative hand value as given by the American Association of TextileChemists and Colorists (AATCC test method “202-2012, Relative Hand Valueof Textiles: Instrumental Method”).

The composition can be in the form of a liquid, a gel, a powder, ahydrocolloid, an aqueous solution, a granule, a tablet, a capsule, asingle compartment sachet, a multi-compartment sachet, a singlecompartment pouch, or a multi-compartment pouch. In some embodiments,the composition is in the form of a liquid, a gel, a powder, a singlecompartment sachet, or a multi-compartment sachet.

In some embodiments, compositions comprising a poly alpha-1,6-glucanderivative as disclosed herein can be in the form of a fabric carecomposition. A fabric care composition can be used for hand wash,machine wash and/or other purposes such as soaking and/or pretreatmentof fabrics, for example. A fabric care composition may take the form of,for example, a laundry detergent; fabric conditioner; any wash-, rinse-,or dryer-added product; unit dose or spray. Fabric care compositions ina liquid form may be in the form of an aqueous composition. In otherembodiments, a fabric care composition can be in a dry form such as agranular detergent or dryer-added fabric softener sheet. Othernon-limiting examples of fabric care compositions can include: granularor powder-form all-purpose or heavy-duty washing agents; liquid, gel orpaste-form all-purpose or heavy-duty washing agents; liquid or dryfine-fabric (e.g. delicates) detergents; cleaning auxiliaries such asbleach additives, “stain-stick”, or pre-treatments; substrate-ladenproducts such as dry and wetted wipes, pads, or sponges; sprays andmists; water-soluble unit dose articles.

The composition can be in any useful form, for example, as powders,granules, pastes, bars, unit dose, or liquid.

The unit dose form may be water-soluble, for example, a water-solubleunit dose article comprising a water-soluble film and a liquid or solidlaundry detergent composition, also referred to as a pouch. Awater-soluble unit dose pouch comprises a water-soluble film which fullyencloses the liquid or solid detergent composition in at least onecompartment. The water-soluble unit dose article may comprise a singlecompartment or multiple compartments. The water-soluble unit dosearticle may comprise at least two compartments or at least threecompartments. The compartments may be arranged in a superposedorientation or in a side-by-side orientation.

A unit dose article is typically a closed structure, made of thewater-soluble film enclosing an internal volume which comprises theliquid or solid laundry detergent composition. The pouch can be of anyform and shape which is suitable to hold and protect the composition,e.g. without allowing the release of the composition from the pouchprior to contact of the pouch to water.

A solid unit dose article is typically a closed structure, made ofwater-soluble fibers enclosing detergent particles and other detergentactives interdispersed between fibers to yield a solid laundry detergentcomposition pad. In another example the solid unit dose article sachetor pouch can comprise a pouch of soluble fibers can be of any form andshape which is suitable to hold and protect the composition, e.g.without allowing the release of the composition from the pouch prior tocontact of the sachet or pouch to water.

The composition may be in the form of a solid, preferably in the form ofparticles, such as a pastille or bead. Suitable particles may comprisethe poly alpha-1,6-glucan ether compound dispersed in a water-solublecarrier. Individual particles may have a mass from about 1 mg to about 1g. The water-soluble carrier may be a water-soluble polymer. Thewater-soluble carrier may be selected from the group consisting ofpolyethylene glycol, sodium acetate, sodium bicarbonate, sodiumchloride, sodium silicate, polypropylene glycol polyoxoalkylene,polyethylene glycol fatty acid ester, polyethylene glycol ether, sodiumsulfate, starch, and mixtures thereof. The composition may comprise fromabout 25% to about 99.99% by weight of the water-soluble carrier, andfrom about 0.01% to about 30% by weight of the poly alpha-1,6-glucanether compound. The particles may further comprise an additional benefitagent, such as a poly alpha-1,6-glucan derivative, a surfactant, aperfume, a conditioning agent (e.g., a quaternary ammonium compoundand/or a silicone), or mixtures thereof. The particles may be firstparticles and may be part of a plurality of particles that furthercomprise second particles. The plurality of particles may include firstparticles and second particles, where the particles that comprise thepoly alpha-1,6-glucan ether compound are the first particles, andwherein the second particles comprise a different benefit agent, such asperfume, which may be unencapsulated perfume, encapsulated perfume, or amixture thereof. The particles may be used in combination with adetergent composition, for example concurrently during a wash cycle, orsubsequently during a rinse cycle.

A liquid detergent composition may be aqueous, typically containing upto about 70% by weight of water and 0% to about 30% by weight of organicsolvent. It may also be in the form of a compact gel type containingless than or equal to 30% by weight water.

The poly alpha-1,6-glucan derivatives disclosed herein can be used as aningredient in the desired product or may be blended with one or moreadditional suitable ingredients and used as, for example, fabric careapplications, laundry care applications, and/or dish care applications.Any of the disclosed compositions, for example, a fabric care, a laundrycare, or a dish care composition can comprise in the range of 0.01 to 99percent by weight of the poly alpha-1,6-glucan derivative, based on thetotal weight of the composition. The composition may comprise 0.1 to 10%or 0.1 to 9% or 0.5 to 8% or 1 to 7% or 1 to 6% or 1 to 5% or 1 to 4% or1 to 3% or 5 to 10% or 10 to 15% or 15 to 20% or 20 to 25% or 25 to 30%or 30 to 35% or 35 to 40% or 40 to 45% or 45 to 50% or 50 to 55% or 55to 60% or 60 to 65% or 65 to 70% or 70 to 75% or 75 to 80% or 80 to 85%or 85 to 90% or 90 to 95% or 95 to 99% by weight of the polyalpha-1,6-glucan derivative, wherein the percentages by weight are basedon the total weight of the composition.

The composition can further comprise at least one of a surfactant, anenzyme, a detergent builder, a complexing agent, a polymer, a soilrelease polymer, a surfactancy-boosting polymer, a bleaching agent, ableach activator, a bleaching catalyst, a fabric conditioner, a clay, afoam booster, a suds suppressor, an anti-corrosion agent, asoil-suspending agent, an anti-soil re-deposition agent, a dye, abactericide, a tarnish inhibitor, an optical brightener, a perfume, asaturated or unsaturated fatty acid, a dye transfer inhibiting agent, achelating agent, a hueing dye, a calcium cation, a magnesium cation, avisual signaling ingredient, an anti-foam, a structurant, a thickener,an anti-caking agent, a starch, sand, a gelling agents, or anycombination thereof. The enzyme may be a cellulase, a protease, anamylase, a lipase, or any combination thereof.

The composition can be a detergent composition useful for, for example,fabric care, laundry care and/or dish care and may further contain oneor more active enzymes. Non-limiting examples of suitable enzymesinclude proteases, cellulases, hemicellulases, peroxidases, lipolyticenzymes (e.g., metallolipolytic enzymes), xylanases, lipases,phospholipases, esterases (e.g., arylesterase, polyesterase),perhydrolases, cutinases, pectinases, pectate lyases, mannanases,keratinases, reductases, oxidases (e.g., choline oxidase),phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, beta-glucanases, arabinosidases,hyaluronidases, chondroitinases, laccases, metalloproteinases,amadoriases, glucoamylases, arabinofuranosidases, phytases, isomerases,transferases, amylases or any combination thereof. If an enzyme(s) isincluded, it may be present in the composition at about 0.0001 to 0.1%by weight of the active enzyme, based on the total weight of thecomposition. In other embodiments, the enzyme can be present at about0.01 to 0.03% by weight of the active enzyme (e.g., calculated as pureenzyme protein) based on the total weight of the composition. In someembodiments, a combination of two or more enzymes can be used in thecomposition. In some embodiments, the two or more enzymes are cellulaseand one or more of proteases, hemicellulases, peroxidases, lipolyticenzymes, xylanases, lipases, phospholipases, esterases, perhydrolases,cutinases, pectinases, pectatelyases, mannanases, keratinases,reductases, oxidases, phenoloxidases, lipoxygenases, ligninases,pullulanases, tannases, pentosanases, malanases, beta-glucanases,arabinosidases, hyaluronidases, chondroitinases, laccases,metalloproteinases, amadoriases, glucoamylases, arabinofuranosidases,phytases, isomerases, transferases, amylases or any combination thereof.

In some embodiments, the composition can comprise one or more enzymes,each enzyme present from about 0.00001% to about 10% by weight, based onthe total weight of the composition. In some embodiments, thecomposition can also comprise each enzyme at a level of about 0.0001% toabout 10%, about 0.001% to about 5%, about 0.001% to about 2% or about0.005% to about 0.5% by weight, based on the total weight of thecomposition.

A cellulase can have endocellulase activity (EC 3.2.1.4), exocellulaseactivity (EC 3.2.1.91), or cellobiase activity (EC 3.2.1.21). Acellulase is an “active cellulase” having activity under suitableconditions for maintaining cellulase activity; it is within the skill ofthe art to determine such suitable conditions. Besides being able todegrade cellulose, a cellulase in certain embodiments can also degradecellulose ether derivatives such as carboxymethyl cellulose.

The cellulase may be derived from any microbial source, such as abacteria or fungus. Chemically-modified cellulases or protein-engineeredmutant cellulases are included. Suitable cellulases include, forexample, cellulases from the genera Bacillus, Pseudomonas, Streptomyces,Trichoderma, Humicola, Fusarium, Thielavia and Acremonium. As otherexamples, the cellulase may be derived from Humicola insolens,Myceliophthora thermophile, Fusarium oxysporum, Trichoderma reesei orany combination thereof. The cellulase, such as any of the foregoing,can be in a mature form lacking an N-terminal signal peptide.Commercially available cellulases useful herein include CELLUSOFT®,CELLUCLEAN®, CELLUZYME® and CAREZYME® (Novozymes A/S); CLAZINASE® andPURADAX® HA and REVITALENZ™ (DuPont Industrial Biosciences), BIOTOUCH®(AB Enzymes); and KAC-500(B)©(Kao Corporation).

Alternatively, a cellulase herein may be produced by any means known inthe art, for example, a cellulase may be produced recombinantly in aheterologous expression system, such as a microbial or fungalheterologous expression system. Examples of heterologous expressionsystems include bacterial (e.g., E. coli, Bacillus sp.) and eukaryoticsystems. Eukaryotic systems can employ yeast (e.g., Pichia sp.,Saccharomyces sp.) or fungal (e.g., Trichoderma sp. such as T. reesei,Aspergillus species such as A. niger) expression systems, for example.

The cellulase in certain embodiments can be thermostable. Cellulasethermostability refers to the ability of the enzyme to retain activityafter exposure to an elevated temperature (e.g. about 60-70° C.) for aperiod of time (e.g., about 30-60 minutes). The thermostability of acellulase can be measured by its half-life (t/2) given in minutes,hours, or days, during which time period half the cellulase activity islost under defined conditions.

The cellulase in certain embodiments can be stable to a wide range of pHvalues (e.g. neutral or alkaline pH such as pH of ˜7.0 to ˜11.0). Suchenzymes can remain stable for a predetermined period of time (e.g., atleast about 15 min., 30 min., or 1 hour) under such pH conditions.

At least one, two, or more cellulases may be included in thecomposition. The total amount of cellulase in a composition hereintypically is an amount that is suitable for the purpose of usingcellulase in the composition (an “effectiveamount”). For example, aneffective amount of cellulase in a composition intended for improvingthe feel and/or appearance of a cellulose-containing fabric is an amountthat produces measurable improvements in the feel of the fabric (e.g.,improving fabric smoothness and/or appearance, removing pills andfibrils which tend to reduce fabric appearance sharpness). As anotherexample, an effective amount of cellulase in a fabric stonewashingcomposition herein is that amount which will provide the desired effect(e.g., to produce a worn and faded look in seams and on fabric panels).The amount of cellulase in a composition herein can also depend on theprocess parameters in which the composition is employed (e.g.,equipment, temperature, time, and the like) and cellulase activity, forexample. The effective concentration of cellulase in an aqueouscomposition in which a fabric is treated can be readily determined by askilled artisan. In fabric care processes, cellulase can be present inan aqueous composition (e.g., wash liquor) in which a fabric is treatedin a concentration that is minimally about 0.01-0.1 ppm total cellulaseprotein, or about 0.1-10 ppb total cellulase protein (e.g., less than 1ppm), to maximally about 100, 200, 500, 1000, 2000, 3000, 4000, or 5000ppm total cellulase protein, for example.

Suitable enzymes are known in the art and can include, for example,MAXATASE®, MAXACAL™, MAXAPEM™, OPTICLEAN®, OPTIMASE®, PROPERASE®,PURAFECT®, PURAFECT® OXP, PURAMAX™, EXCELLASE™, PREFERENZ™ proteases(e.g. P100, P110, P280), EFFECTENZ™ proteases (e.g. P1000, P1050,P2000), EXCELLENZ™ proteases (e.g. P1000), ULTIMASE®, and PURAFAST™(Genencor); ALCALASE®, SAVINASE®, PRIMASE®, DURAZYM™, POLARZYME®,OVOZYME®, KANNASE®, LIQUANASE®, NEUTRASE®, RELASE® and ESPERASE®(Novozymes); BLAP™ and BLAP™ variants (Henkel Kommanditgesellschaft aufAktien, Duesseldorf, Germany), and KAP (B. alkalophilus subtilisin; KaoCorp., Tokyo, Japan) proteases; MANNASTAR®, PURABRITE™, and MANNAWAY®mannanases; M1 LIPASE™, LUMA FAST™, and LIPOMAX™ (Genencor); LIPEX®,LIPOLASE® and LIPOLASE® ULTRA (Novozymes); and LIPASE P™ “Amano” (AmanoPharmaceutical Co. Ltd., Japan) lipases; STAINZYME®, STAINZYME PLUS®,NATALASE®, DURAMYL®, TERMAMYL®, TERMAMYL ULTRA®, FUNGAMYL® and BAN™(Novo Nordisk A/S and Novozymes A/S); RAPIDASE®, POWERASE®, PURASTAR®and PREFERENZ™ (DuPont Industrial Biosciences) amylases; GUARDZYME™(NovoNordisk A/S and Novozymes A/S) peroxidases or any combinationthereof.

The enzymes in the composition can be stabilized using conventionalstabilizing agents, e.g., a polyol such as propylene glycol or glycerol;a sugar or sugar alcohol; lactic acid; boric acid or a boric acidderivative (e.g., an aromatic borate ester).

A detergent composition herein typically comprises one or moresurfactants, wherein the surfactant is selected from nonionicsurfactants, anionic surfactants, cationic surfactants, ampholyticsurfactants, zwitterionic surfactants, semi-polar nonionic surfactantsand mixtures thereof. The surfactant may be petroleum-derived (alsoreferred to as synthetic) or non-petroleum-derived (also referred to asnatural). In some embodiments, the surfactant is present at a level offrom about 0.1% to about 60%, while in alternative embodiments the levelis from about 1% to about 50%, while in still further embodiments thelevel is from about 5% to about 40%, by weight of the cleaningcomposition. A detergent will usually contain 0% to about 50% by weightof an anionic surfactant such as linear alkylbenzenesulfonate (LAS),alpha-olefinsulfonate (AOS), alkyl sulfate (fatty alcohol sulfate) (AS),alcohol ethoxysulfate (AEOS or AES), secondary alkanesulfonates (SAS),alpha-sulfo fatty acid methyl esters, alkyl- or alkenylsuccinic acid, orsoap.

The detergent composition may comprise an alcohol ethoxysulfate of theformula R¹—(OCH₂CH₂)_(x)—O—SO₃M, wherein R¹ is anon-petroleum derived,linear or branched fatty alcohol consisting of even numbered carbonchain lengths of from about C₈ to about C₂₀, and wherein x is from about0.5 to about 8, and where M is an alkali metal or ammonium cation. Thefatty alcohol portion of the alcohol ethoxysulfate (R¹) is derived froma renewable source (e.g., animal or plant derived) rather thangeologically derived (e.g., petroleum-derived). Fatty alcohols derivedfrom a renewable source may be referred to as natural fatty alcohols.Natural fatty alcohols have an even number of carbon atoms with a singlealcohol (—OH) attached to the terminal carbon. The fatty alcohol portionof the surfactant (R¹) may comprise distributions of even number carbonchains, e.g., C12, C14, C16, C18, and so forth.

In addition, a detergent composition may optionally contain 0 wt % toabout 40 wt % of a nonionic surfactant such as alcohol ethoxylate (AEOor AE), carboxylated alcohol ethoxylates, nonylphenol ethoxylate,alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acidmonoethanolamide, fatty acid monoethanolamide, or polyhydroxy alkylfatty acid amide. The detergent composition may comprise an alcoholethoxylate of formula R²—(OCH₂CH₂)_(y)—OH, wherein R² is a non-petroleumderived, linear or branched fatty alcohol consisting of even numberedcarbon chain lengths of from about C₁₀ to about C₁₈, and wherein y isfrom about 0.5 to about 15. The fatty alcohol portion of the alcoholethoxylate (R²) is derived from a renewable source (e.g., animal orplant derived) rather than geologically derived (e.g.,petroleum-derived). The fatty alcohol portion of the surfactant (R²) maycomprise distributions of even number carbon chains, e.g., C12, C14,C16, C18, and so forth.

The composition can further comprise one or more detergent builders orbuilder systems. In some embodiments incorporating at least one builder,the compositions comprise at least about 1%, from about 3% to about 60%or from about 5% to about 40% by weight of the builder, based on thetotal weight of the composition. Builders include, for example, thealkali metal, ammonium and/or alkanolammonium salts of polyphosphates,alkali metal silicates, alkaline earth and alkali metal carbonates,aluminosilicates, polycarboxylate compounds, etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid,and carboxymethyloxysuccinic acid, the various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, citric acid,oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof. Examples of adetergent builder or complexing agent include zeolite, diphosphate,triphosphate, phosphonate, citrate, nitrilotriacetic acid (NTA),ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaaceticacid (DTMPA), alkyl- or alkenylsuccinic acid, soluble silicates orlayered silicates (e.g., SKS-6 from Hoechst). A detergent may also beunbuilt, i.e., essentially free of detergent builder.

The composition can further comprise at least one chelating agent.Suitable chelating agents include, for example, copper, iron and/ormanganese chelating agents and mixtures thereof. In some embodiments inwhich at least one chelating agent is used, the compositions comprisefrom about 0.1% to about 15% or even from about 3% to about 10% byweight of the chelating agent, based on the total weight of thecomposition.

The composition can further comprise at least one deposition aid.Suitable deposition aids include, for example, polyethylene glycol,polypropylene glycol, polycarboxylate, soil release polymers such aspolyterephthalic acid, clays such as kaolinite, montmorillonite,atapulgite, illite, bentonite, halloysite, or any combination thereof.

The composition can further comprise one or more dye transfer inhibitingagents. Suitable dye transfer inhibiting agents include, for example,polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones,polyvinylimidazoles, manganese phthalocyanine, peroxidases,polyvinylpyrrolidone polymers, ethylene-diamine-tetraacetic acid (EDTA);diethylene triamine penta methylene phosphonic acid (DTPMP);hydroxy-ethane diphosphonic acid (HEDP); ethylenediamine N,N′-disuccinicacid (EDDS); methyl glycine diacetic acid (MGDA); diethylene triaminepenta acetic acid (DTPA); propylene diamine tetraacetic acid (PDT A);2-hydroxypyridine-N-oxide (HPNO); or methyl glycine diacetic acid(MGDA); glutamic acid N,N-diacetic acid (N,N-dicarboxymethyl glutamicacid tetrasodium salt (GLDA); nitrilotriacetic acid (NTA);4,5-dihydroxy-m-benzenedisulfonic acid; citric acid and any saltsthereof; N-hydroxyethylethylenediaminetri-acetic acid (HEDTA),triethylenetetraaminehexaacetic acid (TTHA), N-hydroxyethyliminodiaceticacid (HEIDA), dihydroxyethylglycine (DHEG),ethylenediaminetetrapropionic acid (EDTP) and derivatives thereof or anycombination thereof. In embodiments in which at least one dye transferinhibiting agent is used, the compositions can comprise from about0.0001% to about 10%, from about 0.01% to about 5%, or even from about0.10% to about 3% by weight of the dye transfer inhibiting agent, basedon the total weight of the composition.

The composition can further comprise silicates. Suitable silicates caninclude, for example, sodium silicates, sodium disilicate, sodiummetasilicate, crystalline phyllosilicates or any combination thereof. Insome embodiments, silicates can be present at a level of from about 1%to about 20% by weight, based on the total weight of the composition. Inother embodiments, silicates can be present at a level of from about 5%to about 15% by weight, based on the total weight of the composition.

The composition can further comprise dispersants. Suitable water-solubleorganic materials can include, for example, homo- or co-polymeric acidsor their salts, in which the polycarboxylic acid comprises at least twocarboxyl radicals separated from each other by not more than two carbonatoms.

The composition can further comprise one or more other types of polymersin addition to the present poly alpha-1,6-glucan derivatives. Examplesof other types of polymers useful herein include carboxymethyl cellulose(CMC), poly(vinylpyrrolidone) (PVP), polyethylene glycol (PEG),poly(vinyl alcohol) (PVA), polycarboxylates such as polyacrylates,maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acidcopolymers.

The composition can further comprise a bleaching system. For example,the bleaching system can comprise an H₂O₂ source such as perborate,percarbonate, perhydrate salts, mono or tetra hydrate sodium salt ofperborate, persulfate, perphosphate, persilicate, percarboxylic acidsand salts, percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, sulfonated zinc phthalocyanines,sulfonated aluminum phthalocyanines, xanthene dyes which may be combinedwith a peracid-forming bleach activator such as, for example, dodecanoyloxybenzene sulfonate, decanoyl oxybenzene sulfonate, decanoyl oxybenzoicacid or salts thereof, tetraacetylethylenediamine (TAED) ornonanoyloxybenzenesulfonate (NOBS). Alternatively, a bleaching systemmay comprise peroxyacids (e.g., amide, imide, or sulfone typeperoxyacids). In other embodiments, the bleaching system can be anenzymatic bleaching system comprising perhydrolase. Combinations of anyof the above may also be used.

The composition can further comprise conventional detergent ingredientssuch as fabric conditioners, clays, foam boosters, suds suppressors,anti-corrosion agents, soil-suspending agents, anti-soil redepositionagents, dyes, bactericides, tarnish inhibiters, optical brighteners, orperfumes. The pH of a detergent composition herein (measured in aqueoussolution at use concentration) can be neutral or alkaline (e.g., pH ofabout 7.0 to about 11.0).

The composition can be a detergent composition and optionally, a heavyduty (all purpose) laundry detergent composition. In some embodiments,the detergent composition can comprise a detersive surfactant (10%-40%wt/wt), including an anionic detersive surfactant (selected from a groupof linear or branched or random chain, substituted or unsubstitutedalkyl sulphates, alkyl sulphonates, alkyl alkoxylated sulphate, alkylphosphates, alkyl phosphonates, alkyl carboxylates, and/or mixturesthereof), and optionally non-ionic surfactant (selected from a group oflinear or branched or random chain, substituted or unsubstituted alkylalkoxylated alcohol, e.g., C₈-C₁₈ alkyl ethoxylated alcohols and/orC₆-C₁₂ alkyl phenol alkoxylates), where the weight ratio of anionicdetersive surfactant (with a hydrophilic index (HIc) of from 6.0 to 9)to non-ionic detersive surfactant is greater than 1:1. Suitabledetersive surfactants also include cationic detersive surfactants(selected from a group of alkyl pyridinium compounds, alkyl quaternaryammonium compounds, alkyl quaternary phosphonium compounds, alkylternary sulphonium compounds, and/or mixtures thereof); zwitterionicand/or amphoteric detersive surfactants (selected from a group ofalkanolamine sulpho-betaines); ampholytic surfactants; semi-polarnon-ionic surfactants and mixtures thereof.

The composition can be a detergent composition, optionally including,for example, a surfactancy boosting polymer consisting of amphiphilicalkoxylated grease cleaning polymers. Suitable amphiphilic alkoxylatedgrease cleaning polymers can include, for example, alkoxylated polymershaving branched hydrophilic and hydrophobic properties, such asalkoxylated polyalkylenimines, random graft polymers comprising ahydrophilic backbone comprising monomers, for example, unsaturated C₁-C₆carboxylic acids, ethers, alcohols, aldehydes, ketones, esters, sugarunits, alkoxy units, maleic anhydride, saturated polyalcohols such asglycerol, and mixtures thereof; and hydrophobic side chain(s), forexample, one or more C₄-C₂₅ alkyl groups, polypropylene, polybutylene,vinyl esters of saturated C₁-C₆ mono-carboxylic acids, C₁-C₆ alkylesters of acrylic or methacrylic acid, and mixtures thereof.

Suitable heavy duty laundry detergent compositions can optionallyinclude additional polymers such as soil release polymers (includeanionically end-capped polyesters, for example SRP1, polymers comprisingat least one monomer unit selected from saccharide, dicarboxylicacid,polyol and combinations thereof, in random or block configuration,ethylene terephthalate-based polymers and co-polymers thereof in randomor block configuration, for example REPEL-O-TEX SF, SF-2 AND SRP6,TEXCARE SRA100, SRA300, SRN100, SRN170, SRN240, SRN260, SRN300 ANDSRN325, MARLOQUEST SL), anti-redeposition polymers, include carboxylatepolymers, such as polymers comprising at least one monomer selected fromacrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconicacid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonicacid, and any mixture thereof, vinylpyrrolidone homopolymer, and/orpolyethylene glycol, molecular weight in the range of from 500 to100,000 Daltons (Da); and polymeric carboxylate (such asmaleate/acrylate random copolymer or polyacrylate homopolymer). Ifpresent, soil release polymers can be included at 0.1 to 10% by weight,based on the total weight of the composition.

The heavy duty laundry detergent composition can optionally furtherinclude saturated or unsaturated fatty acids, preferably saturated orunsaturated C₁₂-C₂₄ fatty acids; deposition aids, for example,polysaccharides, cellulosic polymers, poly diallyl dimethyl ammoniumhalides (DADMAC), and co-polymers of DADMAC with vinyl pyrrolidone,acrylamides, imidazoles, imidazolinium halides, and mixtures thereof, inrandom or block configuration, cationic guargum, cationic starch,cationic polyacylamides or any combination thereof. If present, thefatty acids and/or the deposition aids can each be present at 0.1% to10% by weight, based on the total weight of the composition.

The detergent composition may optionally include silicone or fatty-acidbased suds suppressors; hueing dyes, calcium and magnesium cations,visual signaling ingredients, anti-foam (0.001% to about 4.0% by weight,based on the total weight of the composition), and/or astructurant/thickener (0.01% to 5% by weight, based on the total weightof the composition) selected from the group consisting of diglyceridesand triglycerides, ethylene glycol distearate, microcrystallinecellulose, microfiber cellulose, biopolymers, xanthan gum, gellan gum,and mixtures thereof).

The compositions disclosed herein can be in the form of a dishwashingdetergent composition. Examples of dishwashing detergents includeautomatic dishwashing detergents (typically used in dishwasher machines)and hand-washing dish detergents. A dishwashing detergent compositioncan be in any dry or liquid/aqueous form as disclosed herein, forexample. Components that may be included in certain embodiments of adishwashing detergent composition include, for example, one or more of aphosphate; oxygen- or chlorine-based bleaching agent; non-ionicsurfactant; alkaline salt (e.g., metasilicates, alkali metal hydroxides,sodium carbonate); any active enzyme disclosed herein; anti-corrosionagent (e.g., sodium silicate); anti-foaming agent; additives to slowdown the removal of glaze and patterns from ceramics; perfume;anti-caking agent (in granular detergent); starch (in tablet-baseddetergents); gelling agent (in liquid/gel based detergents); and/or sand(powdered detergents).

In addition to the poly alpha-1,6-glucan derivative, dishwashingdetergent compositions can comprise (i) a non-ionic surfactant,including any ethoxylated non-ionic surfactant, alcohol alkoxylatedsurfactant, epoxy-capped poly(oxyalkylated) alcohol, or amine oxidesurfactant present in an amount from 0 to 10% by weight; (ii) a builder,in the range of about 5 to 60% by weight, including any phosphatebuilder (e.g., mono-phosphates, di-phosphates, tri-polyphosphates, otheroligomeric-polyphosphates, sodium tripolyphosphate-STPP), anyphosphate-free builder (e.g., amino acid-based compounds includingmethyl-glycine-diacetic acid [MGDA] and salts or derivatives thereof,glutamic-N,N-diacetic acid [GLDA] and salts or derivatives thereof,iminodisuccinic acid (IDS) and salts or derivatives thereof, carboxymethyl inulin and salts or derivatives thereof, nitrilotriacetic acid[NTA], diethylene triamine penta acetic acid [DTPA], B-alaninediaceticacid [B-ADA] and salts thereof), homopolymers and copolymers ofpoly-carboxylic acids and partially or completely neutralized saltsthereof, monomeric polycarboxylic acids and hydroxycarboxylic acids andsalts thereof in the range of 0.5 to 50% by weight, orsulfonated/carboxylated polymers in the range of about 0.1% to about 50%by weight; (iii) a drying aid in the range of about 0.1% to about 10% byweight (e.g., polyesters, especially anionic polyesters, optionallytogether with further monomers with 3 to 6 functionalities, for example,acid, alcohol or ester functionalities which are conducive topolycondensation, polycarbonate-, polyurethane- and/orpolyurea-polyorganosiloxane compounds or precursor compounds thereof,particularly of the reactive cyclic carbonate and urea type); (iv) asilicate in the range from about 1% to about 20% by weight (e.g., sodiumor potassium silicates such as sodium disilicate, sodium meta-silicateand crystalline phyllosilicates); (v) an inorganic bleach (e.g.,perhydrate salts such as perborate, percarbonate, perphosphate,persulfate and persilicate salts) and/or an organic bleach, for example,organic peroxyacids such as diacyl- and tetraacylperoxides, especiallydiperoxydodecanedioic acid, diperoxytetradecanedioic acid, anddiperoxyhexadecanedioic acid; (vi) a bleach activator, for example,organic peracid precursors in the range from about 0.1% to about 10% byweight and/or bleach catalyst (e.g., manganese triazacyclononane andrelated complexes; Co, Cu, Mn, and Fe bispyridylamine and relatedcomplexes; and pentamine acetate cobalt(III) and related complexes);(vii) a metal care agent in the range from about 0.1% to 5% by weight,for example, benzatriazoles, metal salts and complexes, and/orsilicates; and/or (viii) any active enzyme disclosed herein in the rangefrom about 0.01 to 5.0 mg of active enzyme per gram of automaticdishwashing detergent composition, and an enzyme stabilizer component.The percentages by weight are based on the total weight of thecomposition.

In other embodiments, the disclosure relates to a method for treating asubstrate, the method comprising the steps: (A) providing a compositioncomprising a poly alpha-1,6-glucan derivative, the derivativecomprising: (i) poly alpha-1,6-glucan substituted with at least onehydrophobic organic group linked to the poly alpha-1,6-glucan through a—O— linkage moiety; (ii) a weight average degree of polymerization of atleast 5; and (iii) a degree of substitution of about 0.20 to about 1.00(e.g., 0.001-0.60); wherein the poly alpha-1,6-glucan comprises abackbone of glucose monomer units wherein greater than or equal to 40%of the glucose monomer units are linked via alpha-1,6-glycosidiclinkages, and optionally at least 5% of the backbone glucose monomerunits have branches via alpha-1,2- and/or alpha-1,3-glycosidic linkages;(B) contacting the substrate with the composition; and (C) optionallyrinsing the substrate; wherein the substrate is, for example, a textile,a fabric, carpet, upholstery, apparel, or a surface. Optionally, thestep of contacting the substrate can be performed in the presence ofwater. The compositions comprising a poly alpha-1,6-glucan derivativeare as disclosed herein.

In one embodiment, the method of treating the substrate can impartanti-greying properties to the substrate, by which is meant that soilwhich is detached from a fabric during washing of the fabric issuspended in the wash liquor and thus prevented from being redepositedon the fabric. In another embodiment, the method of treating thesubstrate can impart anti-redeposition properties to a substrate. Theeffectiveness of anti-greying and anti-redeposition agents can bedetermined with the use of a tergotometer and multiple washings ofpre-soiled fabrics in the presence of initially clean fabrics which actas redeposition monitors, for example using methods known in the art.

In one embodiment, the substrate can be a textile, a fabric, carpet, orapparel. In another embodiment, the substrate can be carpet, upholstery,or a surface. In yet another embodiment, the substrate can be a textile,a fabric, carpet, upholstery, apparel, or a surface. By “upholstery” ismeant the soft, padded textile covering that is fixed to furniture suchas armchairs and sofas. The treatment provides a benefit to thesubstrate, for example, one or more of improved fabric hand, improvedresistance to soil deposition, improved colorfastness, improved wearresistance, improved wrinkle resistance, improved antifungal activity,improved stain resistance, improved cleaning performance when laundered,improved drying rates, improved dye, pigment or lake update, improvedwhiteness retention, or any combination thereof. The treatment providesa benefit to the substrate, for example improved resistance to soildeposition, improved stain resistance, improved cleaning performance, orany combination thereof.

A fabric herein can comprise natural fibers, synthetic fibers,semi-synthetic fibers, or any combination thereof. A semi-syntheticfiber is produced using naturally occurring material that has beenchemically derivatized, an example of which is rayon. Non-limitingexamples of fabric types herein include fabrics made of (i) cellulosicfibers such as cotton (e.g., broadcloth, canvas, chambray, chenille,chintz, corduroy, cretonne, damask, denim, flannel, gingham, jacquard,knit, matelassé, oxford, percale, poplin, plisse, sateen, seersucker,sheers, terry cloth, twill, velvet), rayon (e.g., viscose, modal,lyocell), linen, and TENCEL®; (ii) proteinaceous fibers such as silk,wool and related mammalian fibers; (iii) synthetic fibers such aspolyester, acrylic, nylon, and the like; (iv) long vegetable fibers fromjute, flax, ramie, coir, kapok, sisal, henequen, abaca, hemp and sunn;and (v) any combination of a fabric of (i)-(iv). Fabric comprising acombination of fiber types (e.g., natural and synthetic) includes thosewith both a cotton fiber and polyester, for example. Materials/articlescontaining one or more fabrics include, for example, clothing, curtains,drapes, upholstery, carpeting, bed linens, bath linens, tablecloths,sleeping bags, tents, carinteriors, etc. Other materials comprisingnatural and/or synthetic fibers include, for example, non-woven fabrics,paddings, paper, and foams. Fabrics are typically of woven or knitconstruction.

The step of contacting can be performed at a variety of conditions, forexample, times, temperatures, wash/rinse volumes. Methods for contactinga fabric or textile substrate, for example, a fabric care method orlaundry method are generally well known. For example, a materialcomprising fabric can be contacted with the disclosed composition: (i)for at least about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, or120 minutes; (ii) at a temperature of at least about 10, 15, 20, 25, 30,35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95° C. (e.g., forlaundry wash or rinse: a “cold” temperature of about 15-30° C., a “warm”temperature of about 30-50° C., a “hot” temperature of about 50-95° C.);(iii) at a pH of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 (e.g., pHrange of about 2-12, or about 3-11); (iv) at a salt (e.g., NaCl)concentration of at least about 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, or4.0% by weight; or any combination of (i)-(iv). The contacting step in afabric care method or laundry method can comprise any of washing,soaking, and/or rinsing steps, for example. In some embodiments, therinsing step is a step of rinsing with water.

Other substrates that can be contacted include, for example, surfacesthat can be treated with a dish detergent (e.g., automatic dishwashingdetergent or hand dish detergent). Examples of such materials includesurfaces of dishes, glasses, pots, pans, baking dishes, utensils andflatware made from ceramic material, china, metal, glass, plastic (e.g.,polyethylene, polypropylene, and polystyrene) and wood (collectivelyreferred to herein as “tableware”). Examples of conditions (e.g., time,temperature, wash volume) for conducting a dishwashing or tablewarewashing method are known in the art. In other examples, a tablewarearticle can be contacted with the composition herein under a suitableset of conditions such as any of those disclosed above with regard tocontacting a fabric-comprising material.

Certain embodiments of a method of treating a substrate further comprisea drying step, in which a material is dried after being contacted withthe composition. The drying step can be performed directly after thecontacting step, or following one or more additional steps that mightfollow the contacting step, for example, drying of a fabric after beingrinsed, in water for example, following a wash in an aqueouscomposition. Drying can be performed by any of several means known inthe art, such as air drying at a temperature of at least about 30, 40,50, 60, 70, 80, 90, 100, 120, 140, 160, 170, 175, 180, or 200° C., forexample. A material that has been dried herein typically has less than3, 2, 1, 0.5, or 0.1 wt % water comprised therein.

The treatment provides a benefit to the substrate, for example improvedresistance to soil deposition, improved stain resistance, improvedcleaning performance, or any combination thereof. The step of contactingcan include wiping or spraying the substrate with the composition.

The following are preferred embodiments of the present invention:

-   1. A laundry care or dish care composition comprising a poly    alpha-1,6-glucan derivative, wherein the poly alpha-1,6-glucan    derivative comprises:    -   (i) a poly alpha-1,6-glucan backbone of glucose monomer units,        wherein greater than or equal to 40% of the glucose monomer        units are linked via alpha-1,6 glycosidic linkages, and        optionally at least 5% of the backbone glucose monomer units        have branches via alpha-1,2 and/or alpha-1,3 glycosidic        linkages; and    -   (ii) at least one hydrophobic organic group linked to the poly        alpha-1,6-glucan backbone through an ether (—O—) linkage moiety;    -   wherein, the poly alpha-1,6-glucan backbone has a weight average        degree of polymerization of at least 5;    -   wherein, the poly alpha-1,6-glucan derivative has a degree of        substitution of ether linkage moiety of from 0.20 to 1.00; and    -   wherein, the wherein the poly alpha-1,6-glucan derivative is        substantially free of hydrophilic substitution.-   2. The composition of embodiment 1, where the hydrophobic organic    group linked to the poly alpha-1,6-glucan backbone through an ether    (—O—) linkage moiety is a hydrophobic group.-   3. The composition of any preceding embodiment, wherein the poly    alpha-1,6-glucan derivative further comprises one or more additional    hydrophobic organic groups linked to the poly alpha-1,6-glucan    backbone through linkage moiety selected from one or more of ester    (—OCO—), carbamate

(˜), sulfonate ester (—OSO₂—), and carbonate ester (—OCOO—).

-   4. The composition of any preceding embodiment, wherein no    hydrophilic organic groups are linked to the poly alpha-1,6-glucan    backbone through the ether (—O—) linkage moiety.-   5. The composition of any preceding embodiment, wherein the poly    alpha-1,6-glucan derivative is substantially free from hydrophilic    groups selected from: carboxylic acid, carboxylic acid salt,    sulfonic acid derivative, sulfonic acid derivative salt, sulfuric    acid derivative, sulfuric acid derivative salt, thiosulfate,    thiosulfate salt, phosphoric acid derivative, phosphoric acid    derivative salt, alkyl amine, alkyl substituted ammonium salt,    quaternized pyridine salt, quaternized imidazole salt, or any    combination thereof.-   6. The composition of any preceding embodiment, wherein the    alpha-1,6-glucan backbone of the poly alpha-1,6-glucan derivative    has a weight average degree of polymerization of either from 5 to    95, or from 125 to 4000.-   7. The composition of any preceding embodiment, wherein, the poly    alpha-1,6-glucan derivative has a degree of substitution of ether    linkage moiety of from 0.40 to 0.90.-   8. The composition of any preceding embodiment, wherein either from    5% to 9%, or from 26% to 40% of the backbone glucose monomer units    have branches via alpha-1,2 or alpha-1,3 glycosidic linkages.-   9. The composition of any preceding embodiment, wherein the    hydrophobic organic group is selected from: a C₁ to C₁₈ alkyl group;    a hydroxy alkyl group; a C₂ to C₁₈ alkenyl group; a C₂ to C₁₈    alkynyl group; a benzyl group; a C₆ to C₂₀ aryl group; a polyether    comprising repeat units of (—CH₂CH₂O—) and/or (—CH₂CH(CH₃)O—)    wherein the total number of repeat units is in the range of 2 to    100; or any combination thereof.-   10. The composition of any preceding embodiment, wherein the    hydrophobic organic group is selected from: a C₁-C₁₀ alkyl group; a    C₁-C₁₀ hydroxyl alkyl group; a polyether comprising repeat units of    (—CH₂CH₂O—), (—CH₂CH(CH₃)O—), (—CH(CH₃)CH(CH₃)O—),    (—CH₂CH(CH₂CH₃)O—), or a mixture thereof, wherein the total number    of repeat units is in the range of 2 to 100; or any combination    thereof.-   11. The composition of any preceding embodiment, wherein the    hydrophobic organic group is a benzyl group, wherein the benzyl    group may be substituted with one or more of: a halogen; a cyano    group; an ester group; an amide group; an ether group; a C₁ to C₆    alkyl group; an aryl group; a C₂ to C₆ alkene group; a C₂ to C₆    alkyne group; or any combination thereof.-   12. The composition of any preceding embodiment, wherein the poly    alpha-1,6-glucan derivative has a biodegradability as determined by    the OECD 301B Ready Biodegradability CO₂ Evolution Test Method of at    least 10% on the 90^(th) day test duration.-   13. The composition of any preceding embodiment, wherein the    composition is in the form of a liquid, a gel, a powder, a    hydrocolloid, an aqueous solution, a granule, a tablet, a capsule, a    single compartment sachet, a pad, a multi-compartment sachet, a    single compartment pouch, or a multi-compartment pouch.-   14. The composition of any preceding embodiment, wherein the    composition further comprising an ingredient selected from:    surfactant, an enzyme, a detergent builder, a complexing agent, a    polymer, a soil release polymer, a surfactancy-boosting polymer, a    bleaching agent, a bleach activator, a bleaching catalyst, a fabric    conditioner, a clay, a foam booster, a suds suppressor, an    anti-corrosion agent, a soil-suspending agent, an anti-soil    re-deposition agent, a dye, a bactericide, a tarnish inhibitor, an    optical brightener, a perfume, a saturated or unsaturated fatty    acid, a dye transfer-inhibiting agent, a chelating agent, a hueing    dye, a calcium cation, a magnesium cation, a visual signaling    ingredient, an anti-foam, a structurant, a thickener, an anti-caking    agent, a starch, sand, a gelling agent, or any combination thereof.-   15. The composition of any preceding embodiment, wherein the    composition comprises an enzyme selected from: a cellulase, a    protease, an amylase, a lipase, or any combination thereof.

Typically, hydrophilic groups include carboxylic acids, carboxylic acidsalts, sulfonic acid derivatives, sulfonic acid derivative salts,sulfuric acid derivatives, sulfuric acid derivative salts, thiosulfate,thiosulfate salts, phosphoric acid derivatives, phosphoric acidderivative salts, alkyl amines, alkyl substituted ammonium salts,quaternized pyridine salts, quaternized imidazole salts, and anycombination thereof.

By hydrophobic substituent, it is typically meant not a hydrophilicsubstituent.

Typically, the hydrophobic organic group is selected from a C₁ to C₁₈alkyl, a C₂ to C₁₈ alkene, a C₂ to C₁₈ alkyne, a polyether comprisingrepeat units of (—CH₂CH₂O—), (—CH₂CH(CH₃)O—), (—CH(CH₃)CH(CH₃)O—),(—CH₂CH(CH₂CH₃)O—), or a mixture thereof, wherein the total number ofrepeat units is in the range of from 2 to 100, a C₆ to C₂₀ aryl, abenzyl, a C₁-C₁₈ alkyl sulfonyl, a C₆-C₂₀ aryl sulfonyl, ap-toluenesulfonyl group, or any combination thereof.

The hydrophobic organic group may be selected from a C₁ to C₁₈ alkyl, abenzyl, a p-toluenesulfonyl group, or any combination thereof. Thehydrophobic organic group may be selected from a benzyl group, and thebenzyl group may be further substituted with one or more of a halogen, acyano, an ester, an amide, an ether group, a C₁ to C₆ alkyl group, anaryl group, a C₂ to C₆ alkene group, a C₂ to C₆ alkyne group, or anycombination thereof.

The hydrophobic organic group may be selected from a C₁ to C₁₈ alkylgroup, a hydroxy alkyl group, a C₂ to C₁₈ alkenyl group, a C₂ to C₁₈alkynyl group, a benzyl group, a C₆ to C₂₀ aryl group, a polyethercomprising repeat units of (—CH₂CH₂O—), (—CH₂CH(CH₃)O—),(—CH(CH₃)CH(CH₃)O—), (—CH₂CH(CH₂CH₃)O—), or a mixture thereof, whereinthe total number of repeat units is in the range of 2 to 100, or anycombination thereof.

The hydrophobic organic group may be selected from a C₁-C₁₀ alkyl group,a C₁-C₁₀ hydroxyl alkyl group, a polyether comprising repeat units of(—CH₂CH₂O—), (—CH₂CH(CH₃)O—), (—CH(CH₃)CH(CH₃)O—), (—CH₂CH(CH₂CH₃)O—),or a mixture thereof, wherein the total number of repeat units is in therange of 2 to 100, or any combination thereof.

The hydrophobic organic group may be selected from C₆-C₂₀ aryl groups,optionally substituted with alkyl groups, the aryl group may preferablybe a tolyl group.

Laundry care and dish care compositions are typically suitable for: (a)the care of finished textiles, cleaning of finished textiles,sanitization of finished textiles, disinfection of finished textiles,detergents, stain removers, softeners, fabric enhancers, stain removalor finished textiles treatments, pre and post wash treatments, washingmachine cleaning and maintenance, with finished textiles intended toinclude garments and items made of cloth; (b) the care of dishes,glasses, crockery, cooking pots, pans, utensils, cutlery and the like inautomatic, in-machine washing, including detergents, preparatory posttreatment and machine cleaning and maintenance products for both thedishwasher, the utilized water and its contents; or (c) manual hand dishwashing detergents.

The following example formulations are suitable for the presentinvention:

The following are illustrative examples of cleaning compositionsaccording to the present disclosure and are not intended to be limiting.

Examples 1-7: Heavy Duty Liquid Laundry Detergent Compositions

In- 1 2 3 4 5 6 7 gredients % weight AE_(1.8)S 6.77 5.16 1.36 1.30 — — —AE₃S — — — — 0.45 — — LAS 0.86 2.06 2.72 0.68 0.95 1.56 3.55 HSAS 1.852.63 1.02 — — — — AE9 6.32 9.85 10.20 7.92 AE8 35.45 AE7 8.40 12.44C₁₂₋₁₄ 0.30 0.73 0.23 0.37 — — — dimethyl Amine Oxide C₁₂₋₁₈ 0.80 1.900.60 0.99 1.20 — 15.00 Fatty Acid Citric 2.50 3.96 1.88 1.98 0.90 2.500.60 Acid Optical 1.00 0.80 0.10 0.30 0.05 0.50 0.001 Brightener 1Optical  0.001 0.05 0.01 0.20 0.50 — 1.00 Brightener 3 Sodium 1.60 0.091.20 0.04 1.60 1.20 0.20 formate DTI 0.32 0.05 — 0.60 — 0.60 0.01 Sodium2.30 3.80 1.70 1.90 1.70 2.50 2.30 hydroxide Mono- 1.40 1.49 1.00 0.70 —— — ethanol- amine Diethylene 5.50 — 4.10 — — — — glycol Chelant 1 0.150.15 0.11 0.07 0.50 0.11 0.80 4-formyl- — — — — 0.05 0.02 0.01 phenyl-boronic acid Sodium 1.43 1.50 1.10 0.75 — 1.07 — tetraborate Ethanol1.54 1.77 1.15 0.89 — 3.00 7.00 Polymer 1 0.10 — — — — — 2.00 Polymer 20.30 0.33 0.23 0.17 — — — Polymer 3 — — — — — — 0.80 Polymer 4 0.80 0.810.60 0.40 1.00 1.00 — Polymer 5 0.50 1.00 2.00 2.50 3.00 2.50 1.50(poly- glucans) 1,2-Pro- — 6.60 — 3.30 0.50 2.00 8.00 panediolStructurant 0.10 — — — — — 0.10 Perfume 1.60 1.10 1.00 0.80 0.90 1.501.60 Perfume 0.10 0.05 0.01 0.02 0.10 0.05 0.10 en- capsulate Protease0.80 0.60 0.70 0.90 0.70 0.60 1.50 Man- 0.07 0.05 0.045 0.06 0.04 0.0450.10 nanase Amylase 1 0.30 — 0.30 0.10 — 0.40 0.10 Amylase 2 — 0.20 0.100.15 0.07 — 0.10 Xylo- 0.20 0.10 — — 0.05 0.05 0.20 glucanase Lipase0.40 0.20 0.30 0.10 0.20 — — Polishing — 0.04 — — — 0.004 — enzymeNuclease 0.05 — — — — — 0.003 Dispersin — — — 0.05 0.03 0.001 0.001 BLiquitinto 0.01 — — — — — 0.005 V200 Leuco 0.05  0.035 0.01 0.02 0.0040.002 0.004 colorant Dye — 0.3  — 0.03 — 0.3 0.3 control agent Water,Balance dyes & minors pH 8.2Based on total cleaning and/or treatment composition weight. Enzymelevels are reported as raw material.

-   AE1.8 S is C₁₂₋₁₅ alkyl ethoxy (1.8) sulfate-   AE3 S is C₁₂₋₁₅ alkyl ethoxy (3) sulfate-   AE7 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 7-   AE8 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 8-   AE9 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 9-   Amylase 1 is Stainzyme®, 15 mg active/g, supplied by Novozymes-   Amylase 2 is Natalase®, 29 mg active/g, supplied by Novozymes-   Xyloglucanase is Whitezyme®, 20 mg active/g, supplied by Novozymes-   Chelant 1 is diethylene triamine pentaacetic acid-   Chelant 2 is 1-hydroxyethane 1,1-diphosphonic acid-   Dispersin B is a glycoside hydrolase, reported as 1000 mg active/g-   DTI is either poly(4-vinylpyridine-1-oxide) (such as Chromabond    S-403E®), or poly(1-vinylpyrrolidone-co-1-vinylimidazole) (such as    Sokalan HP56®).-   Dye control agent Dye control agent in accordance with the    invention, for example Suparex® O.IN (M1), Nylofixan® P (M2),    Nylofixan® PM (M3), or Nylofixan® HF (M4)-   HSAS is mid-branched alkyl sulfate as disclosed in U.S. Pat. Nos.    6,020,303 and 6,060,443-   LAS is linear alkylbenzenesulfonate having an average aliphatic    carbon chain length C₉-C₁₅ (HLAS is acid form).-   Leuco colorant Any suitable leuco colorant or mixtures thereof    according to the instant invention.-   Lipase is Lipex®, 18 mg active/g, supplied by Novozymes-   Liquitint® V200 is a thiophene azo dye provided by Milliken-   Mannanase is Mannaway®, 25 mg active/g, supplied by Novozymes-   Nuclease is a Phosphodiesterase SEQ ID NO 1, reported as 1000 mg    active/g-   Optical Brightener 1 is disodium    4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate-   Optical Brightener 3 is Optiblanc SPL10® from 3V Sigma-   Perfume encapsulate is a core-shell melamine formaldehyde perfume    microcapsules.-   Polishing enzyme is Para-nitrobenzyl esterase, reported as 1000 mg    active/g-   Polymer 1 is    bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₅O)(C₂H₄O)n),    wherein n=20-30, x=3 to 8 or sulphated or sulfonated variants    thereof-   Polymer 2 is ethoxylated (EO₁₅) tetraethylene pentamine-   Polymer 3 is ethoxylated polyethylenimine-   Polymer 4 is ethoxylated hexamethylene diamine-   Polymer 5 is modified polyglucans of this invention-   Protease is PurafectPrime®, 40.6 mg active/g, supplied by DuPont-   Structurant is Hydrogenated Castor Oil

The following is a suitable water-soluble unit dose formulation. Thecomposition can be part of a single chamber water soluble unit dosearticle or can be split over multiple compartments resulting in below“averaged across compartments” full article composition.

Composition Ingredients 1 (wt %) Fatty alcohol ethoxylate non-ionicsurfactant, 3.8 C₁₂₋₁₄ average degree of ethoxylation of 7 LutensolXL100 0.5 Linear C₁₁₋₁₄ alkylbenzene sulphonate 24.6 AE3S Ethoxylatedalkyl sulphate with an average degree of ethoxylation of 3 12.5 Citricacid 0.7 Palm Kernel Fatty acid 5.3 Nuclease enzyme (wt % activeprotein) 0.01 Protease enzyme (wt % active protein) 0.07 Amylase enzyme(wt % active protein) 0.005 Xyloglucanese enzyme (wt % active protein)0.005 Mannanase enzyme (wt % active protein) 0.003 Ethoxylatedpolyethyleneimine 1.6 Amphiphilic graft copolymer 2.6 Zwitterionicpolyamine 1.8 Polyglucan of the present invention 5.0 Anionic polyesterterephthalate 0.6 HEDP 2.2 Brightener 49 0.4 Silicone anti-foam 0.3Hueing dye 0.05 1,2 PropaneDiol 12.3 Glycerine 4.7 DPG(DiPropyleneGlycol) 1.7 TPG (TriPropyleneGlycol) 0.1 Sorbitol 0.1Monoethanolamine 10.2 K2SO3 0.4 MgCl2 0.3 Water 10.8 Hydrogenated castoroil 0.1 Perfume 2.1 Aesthetic dye & Minors Balance to 100 pH (10%product concentration in 7.4 demineralized water at 20° C.)

Solid free-flowing particulate laundry detergent composition examples:

Ingredient Amount (in wt %) Anionic detersive surfactant (such as alkylbenzene from 8 wt % to 15 wt % sulphonate, alkyl ethoxylated sulphateand mixtures thereof) Non-ionic detersive surfactant (such as alkylethoxylated from 0.1 wt % to 4 wt % alcohol) Cationic detersivesurfactant (such as quaternary from 0 wt % to 4 wt % ammonium compounds)Other detersive surfactant (such as zwiterionic detersive from 0 wt % to4 wt % surfactants, amphoteric surfactants and mixtures thereof)Carboxylate polymer (such as co-polymers of maleic acid from 0.1 wt % to4 wt % and acrylic acid and/or carboxylate polymers comprising ethermoieties and sulfonate moieties) Polyethylene glycol polymer (such as apolyethylene glycol from 0 wt % to 4 wt % polymer comprising polyvinylacetate side chains) Polyester soil release polymer (such as Repel-o-texand/or from 0 wt % to 2 wt % Texcare polymers) Cellulosic polymer (suchas carboxymethyl cellulose, from 0.5 wt % to 2 wt % methyl cellulose andcombinations thereof) Polyglucan of the present invention From 0.1 wt %to 8 wt % Other polymer (such as care polymers) from 0 wt % to 4 wt %Zeolite builder and phosphate builder (such as zeolite 4A from 0 wt % to4 wt % and/or sodium tripolyphosphate) Other co-builder (such as sodiumcitrate and/or citric acid) from 0 wt % to 3 wt % Carbonate salt (suchas sodium carbonate and/or sodium from 0 wt % to 20 wt % bicarbonate)Silicate salt (such as sodium silicate) from 0 wt % to 10 wt % Filler(such as sodium sulphate and/or bio-fillers) from 10 wt % to 70 wt %Source of hydrogen peroxide (such as sodium percarbonate) from 0 wt % to20 wt % Bleach activator (such as tetraacetylethylene diamine from 0 wt% to 8 wt % (TAED) and/or nonanoyloxybenzenesulphonate (NOBS)) Bleachcatalyst (such as oxaziridinium-based bleach from 0 wt % to 0.1 wt %catalyst and/or transition metal bleach catalyst) Other bleach (such asreducing bleach and/or pre-formed from 0 wt % to 10 wt % peracid)Photobleach (such as zinc and/or aluminium sulphonated from 0 wt % to0.1 wt % phthalocyanine) Chelant (such asethylenediamine-N′N′-disuccinic acid from 0.2 wt % to 1 wt % (EDDS)and/or hydroxyethane diphosphonic acid (HEDP)) Hueing agent (such asdirect violet 9, 66, 99, acid red 50, from 0 wt % to 1 wt % solventviolet 13 and any combination thereof) Brightener (CI. fluorescentbrightener 260 or C.I. from 0.1 wt % to 0.4 wt % fluorescent brightener351) Protease (such as Savinase, Savinase Ultra, Purafect, FN3, from 0.1wt % to 0.4 wt % FN4 and any combination thereof) Amylase (such asTermamyl, Termamyl ultra, Natalase, from 0 wt % to 0.2 wt % Optisize,Stainzyme, Stainzyme Plus and any combination thereof) Cellulase (suchas Carezyme and/or Celluclean) from 0 wt % to 0.2 wt % Lipase (such asLipex, Lipolex, Lipoclean and any from 0 wt % to 1 wt % combinationthereof) Other enzyme (such as xyloglucanase, cutinase, pectate from 0wt % to 2 wt % lyase, mannanase, bleaching enzyme) Fabric softener (suchas montmorillonite clay and/or from 0 wt % to 15 wt %polydimethylsiloxane (PDMS)) Flocculant (such as polyethylene oxide)from 0 wt % to 1 wt % Suds suppressor (such as silicone and/or fattyacid) from 0 wt % to 4 wt % Perfume (such as perfume microcapsule,spray-on perfume, from 0.1 wt % to 1 wt % starch encapsulated perfumeaccords, perfume loaded zeolite, and any combination thereof) Aesthetics(such as coloured soap rings and/or coloured from 0 wt % to 1 wt %speckles/noodles) Miscellaneous balance to 100 wt %

EXAMPLES

Unless otherwise stated, all ingredients are available fromSigma-Aldrich, St. Louis, Mo. and were used as received.

As used herein, “Comp. Ex.” Means Comparative Example; “Ex.” meansExample; “std dev” means standard deviation; “g” means gram(s); “mL”means milliliter(s); “uL” means microliter(s); “wt” means weight; “L”means liter(s); “min” means minute(s); “kDa” means kilodaltons; “PES”means polyethersulfone.

Method for Determining Anomeric Linkages by NMR Spectroscopy

Glycosidic linkages in water soluble oligosaccharides and polysaccharideproducts synthesized by a glucosyltransferase GTF8117 and alpha-1,2branching enzyme were determined by ¹H NMR (Nuclear Magnetic ResonanceSpectroscopy). Dry oligosaccharide/polysaccharide polymer (6 mg to 8 mg)was dissolved in a solution of 0.7 mL of 1 mM DSS(4,4-dimethyl-4-silapentane-1-sulfonic acid; NMR reference standard) inD₂O. The sample was stirred at ambient temperature overnight. 525 uL ofthe clear homogeneous solution was transferred to a 5 mm NMR tube. 2D¹H, ¹³C homo/hetero-nuclear suite of NMR experiments were used toidentify AGU (anhydroglucose unit) linkages. The data were collected at20° C. and processed on a Bruker Avance III NMR spectrometer, operatingat either 500 MHz or 600 MHz. The systems are equipped with a protonoptimized, helium cooled cryoprobe. The 1D ¹H NMR spectrum was used toquantify glycosidic linkage distribution and finds the polysaccharidebackbone as primarily alpha-1,6. The results reflect the ratio of theintegrated intensity of a NMR resonance representing an individuallinkage type divided by the integrated intensity of the sum of all peakswhich represent glucose linkages, multiplied by 100.

Water Solubility Test Method

The following method was used to determine if a poly alpha-1,6-glucanderivative was water soluble. The derivative was suspended at adetermined weight in deionized water and shaken or stirred overnight atroom temperature. The polymer is soluble if no solid is detected.

Biodegradation Test Method

The biodegradability of the polysaccharide derivative was determinedfollowing the OECD 301B Ready Biodegradability CO₂ Evolution TestGuideline. In this study, the test substance is the sole carbon andenergy source and under aerobic conditions microorganisms metabolize thetest substance producing CO₂ or incorporating the carbon into biomass.The amount of CO₂ produced by the test substance (corrected for the CO₂evolved by the blank inoculum) is expressed as a percentage of thetheoretical amount of CO₂ (ThCO₂) that could have been produced if theorganic carbon in the test substance was completely converted to CO₂.

Method for Evaluating Whiteness Performance of Polymers

Whiteness maintenance, also referred to as whiteness preservation, isthe ability of a detergent to keep white items from whiteness loss whenthey are washed in the presence of soils. White garments can becomedirty/dingy looking over time when soils are removed from dirty clothesand suspended in the wash water, then these soils can re-deposit ontoclothing, making the clothing less white each time they are washed. Thewhiteness benefit of poly alpha-1,6-glucan derivatives is evaluatedusing automatic Miniwasher with 5 pots. SBL2004 test soil stripssupplied by WFK Testgewebe GmbH are used to simulate consumer soillevels (mix of body soil, food, dirt, grass etc.). On average, every 1SBL2004 strip is loaded with 8 g soil. White Fabric swatches of Table 2below purchased from WFK Testgewebe GmbH are used as whiteness tracers.Before wash test, L, a, b values of all whiteness tracers are measuredusing a Konica Minolta CM-3610D spectrophotometer.

TABLE 2 White Fabric Swatches White- White- Fiber ness ness % Con-Fabric Index Index Fiber struc- Density (WI) (WI) Code Content tion(g/m) A* D65** Size Cotton 100 Woven ~540 ~93 ~163 8″ × 8″ Terry (20 ×20 cm) Cotton 100 Weft ~220 ~96 ~165 8″ × 8″ Knit Knit (20 × 20 cm)Polyester/ 65/35 Plain ~125 ~98 ~156 8″ × 8″ Cotton Woven (20 × 20 cm)Polyester 100 Weft ~200 ~95 ~156 8″ × 8″ Knit (20 × 20 cm) Cotton/ 98/2 Woven ~180 ~86 ~158 8″ × 8″ Spandex Twill (20 × 20 cm) *WI(A)—illuminantA (indoor lighting) **WI(D65)—illuminant D65 (outdoor lighting)

Three cycles of wash are needed to complete the test:

Cycle 1: desired amount of detergent is fully dissolved by mixing with7.57 L water (at defined hardness) in each Miniwasher tube. 3.5 SBL2004strips (˜28 g of soil) and 3 whiteness tracers (internal replicate) ofeach fabric type are washed and rinsed in the Miniwasher under definedconditions, then dried.Cycle 2: The above whiteness tracers are washed again with new set ofSBL2004 sheet, and dried. All other conditions remain same as cycle 1.Cycle 3: The above whiteness tracers are washed again with new set ofSBL2004 sheet, and dried. All other conditions remain same as cycle 1.

After Cycle 3, all whiteness tracers are dried and then measured againusing Konica Minolta CM-3610D spectrophotometer. The changes inWhiteness Index (ΔWI(CIE)) are calculated based on L, a, b measurebefore and after wash:ΔWI(CIE)═WI(CIE)(after wash)−WI(CIE)(before wash).

Miniwasher have 5 pots, 5 products can be tested in one test. In atypical polymer whiteness performance test, one reference productcontains comparative polymer or no polymer is tested together with 4products containing inventive polyglucan derivatives as disclosedherein, and “ΔWI versus reference” is reported.ΔWI(CIE) versus reference=ΔWI(CIE)(product)−ΔWI(CIE)(reference)Representative Preparation of Poly Alpha-1,3-Glucan

Poly alpha-1,3-glucan can be prepared using a gtfJ enzyme preparation asdescribed in U.S. Pat. No. 7,000,000; U. S. Patent Appl. Publ. No.2013/0244288, now U.S. Pat. No. 9,080,195; and U.S. Patent Appl. Publ.No. 2013/0244287, now U.S. Pat. No. 8,642,757 (all of which areincorporated herein by reference in their entirety).

Poly alpha-1,3-glucan polymer can be synthesized following theprocedures disclosed in U. S. Appl. Publ. No. 2014/0179913, now U.S.Pat. No. 9,139,718 (see Example 12 therein, for example), both of whichare incorporated herein by reference in their entirety.

Preparation of Poly Alpha-1,6-Glucan Samples

Methods to prepare poly alpha-1,6-glucan containing various amounts ofalpha-1,2 branching are disclosed in published patent applicationWO2017/091533, which is incorporated herein by reference. Reactionparameters such as sucrose concentration, temperature, and pH can beadjusted to provide poly alpha-1,6-glucan having various levels ofalpha-1,2-branching and molecular weight. A representative procedure forthe preparation of alpha-1,2-branched poly alpha-1,6-glucan is providedbelow (containing 19% alpha-1,2-branching and 81% alpha-1,6 linkages).The 1D ¹H NMR spectrum was used to quantify glycosidic linkagedistribution. Additional samples of poly alpha-1,6-glucan withalpha-1,2-branching were prepared similarly. For example, one samplecontained 32% alpha-1,2-branching and 68% alpha-1,6 linkages, andanother contained 10% alpha-1,2-branching and 90% alpha-1,6 linkages.

Preparation of Poly Alpha-1,6-Glucan with 19% Alpha-1,2 Branching

Soluble alpha-1,2-branched poly alpha-1,6-glucan was prepared usingstepwise combination of glucosyltransferase GTF8117 and alpha-1,2branching enzyme GTFJ18T1, according to the following procedure.

A reaction mixture (2 L) comprised of sucrose (450 g/L), GTF8117 (9.4U/mL), and 50 mM sodium acetate was adjusted to pH 5.5 and stirred at47° C. Aliquots (0.2-1 mL) were withdrawn at predetermined times andquenched by heating at 90° C. for 15 min. The resulting heat-treatedaliquots were passed through 0.45-μm filter. The flow-through wasanalyzed by HPLC to determine the concentration of sucrose, glucose,fructose, leucrose, oligosaccharides and polysaccharides. After 23.5 h,the reaction mixture was heated to 90° C. for 30 minutes. An aliquot ofthe heat-treated reaction mixture was passed through 0.45-μm filter andthe flow-through was analyzed for soluble mono/disaccharides,oligosaccharides, and polysaccharides. A major product was lineardextran with a DPw of 93.

A second reaction mixture was prepared by adding 238.2 g of sucrose and210 mL of alpha-1,2-branching enzyme GTFJ18T1 (5.0 U/mL) to the leftoverheat-treated reaction mixture that was obtained from the GTF8117reaction described immediately above. The mixture was stirred at 30° C.with a volume of ˜2.2 L. Aliquots (0.2-1 mL) were withdrawn atpredetermined times and quenched by heating at 90° C. for 15 min. Theresulting heat-treated aliquots were passed through 0.45-μm filter. Theflow-through was analyzed by HPLC to determine the concentration ofsucrose, glucose, fructose, leucrose, oligosaccharides andpolysaccharides. After 95 h, the reaction mixture was heated to 90° C.for 30 minutes. An aliquot of the heat-treated reaction mixture waspassed through 0.45-μm filter and the flow-through was analyzed forsoluble mono/disaccharides, oligosaccharides, and polysaccharides.Leftover heat-treated mixture was centrifuged using 1 L centrifugationbottles. The supernatant was collected and cleaned more than 200-foldusing ultrafiltration system with 1 or 5 KDa MWCO cassettes anddeionized water. The cleaned oligo/polysaccharide product solution wasdried. Dry sample was then analyzed by ¹H NMR spectroscopy to determinethe anomeric linkages of the oligosaccharides and polysaccharides.

Comparative Polymer Example 1

Modification of Poly Alpha-1,3-Glucan (DPw 800) with Benzyl Chloride atLow DoS (DoS=0.17)

To a 4-neck 2 liter flask was added with stirring 980 mL of water and,portion-wise, poly alpha-1,3-glucan (270 g of 40 wt % solid). Sodiumhydroxide (55 g of 50 wt % aqueous solution) was added dropwise over a10-minute period while the reaction mixture was stirred at 20-25° C.,then at room temperature for 2 hours. The reaction mixture was heated to75° C. and benzyl chloride (77 g) was added. The reaction mixture washeated to 85° C. and kept at 85° C. for 3.5 hours. The reaction mixturewas cooled and filtered. The wet cake was washed with water (3×700 mL),ethanol (50 wt %, 800 mL), methanol (80 wt %, 800 mL), acetone (800 mL),and hexanes (2×500 mL). The resulting wet cake was dried on frit withvacuum and N₂ purge for 3 hours to afford a white solid. The solid wasdried in vacuum oven at 80° C. overnight with nitrogen sweep to give awhite solid, 96 g. The degree of benzyl substitution was determined by¹H NMR analysis to be 0.17. This material is not water soluble at 0.1 wt%.

Inventive Polymer Example 1 (DoS=0.26)

Modification of Poly Alpha-1,6-Glucan with Benzyl Chloride

Poly alpha-1,6-glucan (20 kDa, 27% alpha-1,2-branching and 73% alpha 1,6linkages, 100 g, 6% water content) was added to water (150 mL) portionby portion at room temperature while the aqueous phase was stirred. Themixture was stirred at room temperature until solids were dissolved.Sodium hydroxide solution (24.5 g, 50 wt %) was added to the solution atroom temperature. Slight yellow color was observed. The reaction mixturewas heated to 72° C. (the color darkened to brownish) and benzylchloride (32 g) was added. The reaction mixture was stirred at 75-80° C.for 3 hours. Water (500 mL) was added and the pH of the resultingmixture was adjusted to about 7 by HCl (18.5 wt. %, 4.3 g). Then themixture was diluted with water to a total volume of about 3 L, which wasfiltered to remove any solids. The filtrate was purified onultra-filtration (10K membrane). The retentant was concentrated andwashed with isopropyl alcohol (IPA), dried on the filter with N₂ flash,then in a 40° C. vacuum oven overnight with nitrogen flash, then underfull vacuum (0.1 mm Hg) at 50° C. for 6 hours to give a solid (100.5 g).Based on ¹H NMR analysis, the DoS was 0.26 (benzyl group). This materialis water soluble at greater than 0.1 wt %.

Inventive Polymer Example 2 (DoS=0.25)

Modification of Poly Alpha-1,6-Glucan with 1,2-Epoxy-3-Phenoxypropane

Poly alpha-1,6-glucan powder (21 kDa, 31% alpha-1,2-branching and 69%alpha-1,6 linkages, 20 g) was dissolved in 50 mL deionized (DI) water ina 3 neck flask under N₂. To this was added sodium hydroxide solution (50wt %, 6 g) and the mixture was stirred at room temperature for 15 min toyield a yellow solution. To this was added 1,2-epoxy-3-phenoxypropane (9g). The mixture was heated to 70° C. under nitrogen for 4 hours, thencooled overnight under N₂, yielding a white gummy (stirrable) material.To this was added 20 mL water, and the mixture was heated to 70° C. foranother 6 hours. The gummy material was diluted with approximately 50 mLwater, and neutralized with 18 wt % HCl. The product was further dilutedto about 1.5 L water, filtered (no visible solid collected), purified byTFF (MWCO 10 kD, 3 membranes with about 4× diafiltration volume), andfreeze-dried to yield a light tan solid. The degree of substitution wasdetermined by ¹H NMR analysis to be 0.25. This material is water solubleat greater than 0.1 wt %.

Inventive Polymer Example 3 (DoS=0.70)

Modification of Poly Alpha-1,6-Glucan with Allyl Glycidyl Ether

Poly alpha-1,6-glucan powder (15 kDa, 9% alpha-1,2-branching and 910alpha-1,6 linkages, 20 g) was dissolved in 100 mL deionized water in a 3neck flask. The solution was cooled to 0-5° C. To this was added 21 g 50wt % sodium hydroxide solution. The solution was stirred for 15 min. Tothis was added allyl glycidyl ether (58 g) dropwise via the additionalfunnel. The mixture was heated to 65° C. under nitrogen for 6 hours. Theamber solution was cooled, neutralized to pH 7 with 18 wt % HCl. Thelight yellow solution was diluted to 1.5 L, purified by nanofiltration(3× MWCO 5 kD, approx. 6 L of water was passed through). The solutionwas concentrated by rotavap and freeze dried to yield a white powder.The degree of substitution was determined by ¹H NMR analysis to be 0.70.This material is water soluble.

Inventive Polymer Example 4 (DoS=0.20)

Modification of Poly Alpha-1,6-Glucan with Glycidyl Triethylene GlycolMonomethyl Ether

Poly alpha-1,6-glucan (21 kDa, 31% alpha-1,2-branching and 6869% alpha1,6-linkages, 20 g) was dissolved in 50 mL dd water. The solution wascooled to 0-5° C. in an ice/water bath under nitrogen. To this was added9.8 g of 50 wt % sodium hydroxide solution via the additional funnel.The mixture was stirred at 5° C. for 15 min. To this was added glycidyltriethylene glycol (27 g). The ice bath was removed. The mixture washeated to 65° C. under nitrogen for 6 hours. The mixture was neutralizedwith HCl and purified by nanofiltration (MWCO 5 kD), freeze-dried toyield a white solid. The degree of substitution was determined by ¹H NMRanalysis to be 0.20. This material is water soluble at greater than 0.1wt %.

Inventive Polymer Example 5 (DoS=0.23)

Modification of Poly Alpha-1,6-Glucan with Benzyl Chloride

Poly alpha-1,6-glucan (17 kDa, 18% alpha-1,2-branching and 82% alpha 1,6linkages, 100 g, 5% water content) was added to water (150 mL) portionby portion at room temperature with stirring. The mixture was stirred atroom temperature until solids were dissolved. Sodium hydroxide solution(26.3 g, 50 wt %) was added to the solution at room temperature. Slightyellow color was observed. The reaction mixture was heated to 71° C.(the color darkened to brownish) and benzyl chloride (34.1 g) was added.The reaction mixture was stirred at 70-75° C. for 3 hours. Water (500mL) was added and the pH of the resulting mixture was adjusted to about7 by HCl (18.5 wt. %). Then the mixture was diluted with water to totalvolume about 3 L, which was filtered to remove any solids. The filtratewas purified by ultra-filtration (10K membrane). The product wasconcentrated and dried to give a solid (92.7 g). Based on ¹H NMRanalysis, its DoS was 0.23. This material is water soluble at greaterthan 0.1 wt %.

Inventive Polymer Example 6 (DoS=0.25)

Modification of Poly Alpha-1,6-Glucan with Styrene Oxide

A 4-neck, 250 mL round bottom flask containing a stir rod, thermocouple,addition funnel and condenser with N₂ inlet on top was charged with 36.7g of poly alpha-1,6-glucan (17 kDa, 18% alpha-1,2-branching and 82%alpha-1,6 linkages) and water (60 mL). The mixture was stirred at roomtemperature overnight to dissolve the solid. The mixture was stirredwhile 2.64 g of 50 wt. % sodium hydroxide solution was added over a5-minute period. The reaction mixture was heated with an 85° C. oil bathfor one hour. Styrene oxide (10.4 g) was added in 5 min. The reactionwas allowed to stir for 3-4 hours at in the 85° C. oil bath. Thetemperature was cooled to 25° C. The pH of the mixture was adjusted toabout 7 by the addition of 18.5 wt. % hydrochloric acid. The mixture wasdiluted with water to about 800 mL in total volume and filtered througha 0.22 micron filter. The filtrate was further purified byultrafiltration (10K membrane). The product was concentrated and driedto give a solid. ¹H NMR analysis indicated the DoS as 0.25.

Inventive Polymer Example 7 (DoS=0.24)

Modification of Poly Alpha-1,6-Glucan with Styrene Oxide

A 4-neck, 250 mL round bottom flask containing a stir rod, thermocouple,addition funnel and condenser with N₂ inlet on top was charged with 10.5g (61.7 mmoles) of powder glucan (68 kDa, 33% alpha-1,2-branching and67% alpha-1,6 linkages), and water (18 mL). The mixture was stirred atroom temperature overnight to dissolve the solid. The mixture wasstirred while 0.65 g (8 mmoles NaOH) of 50 wt. % sodium hydroxidesolution was added over a 5-minute period. The reaction mixture washeated with an 85° C. oil bath for one hour. Styrene oxide (4.5 g, 37.5mmoles) was added in 5 min. The reaction was allowed to stir for 3-4hours at in the 85° C. oil bath. The temperature was cooled to 25° C.The pH of the mixture was adjusted to about 7 by the addition of 18.5wt. % hydrochloric acid. The mixture was diluted with water to about 800mL in total volume and filtered through a 0.22 micron filter. Thefiltrate was further purified by ultrafiltration (10K membrane). Theproduct was concentrated and dried to give a solid (10 g). ¹H NMRanalysis indicated the DoS as 0.24. The material is soluble at greaterthan 0.1 wt %.

Inventive Polymer Example 8 (DoS=0.30)

Modification of Poly Alpha-1,6-Glucan with Allyl Glycidyl Ether

Poly alpha-1,6-glucan powder (15 kDa, 9% alpha-1,2-branching and 91%alpha-1,6 linkages, 41 g) was dissolved in 100 mL deionized water in a 3neck flask. The solution was cooled to 0-5° C. To this was added 21 g 50wt % sodium hydroxide solution. The solution was stirred for 15 min. Tothis was added allyl glycidyl ether (29 g) dropwise via the additionalfunnel. The mixture was heated to 65° C. under nitrogen for 6 hours. Theamber solution was cooled, neutralized to pH 7 with 18 wt % HCl. Thelight yellow solution was diluted to 1.5 L, purified by ultrafiltration(3×MWCO 5 kD, approx. 6 L of water was passed through). The solution wasconcentrated by rotavap and freeze dried to yield a white powder. Thedegree of substitution was determined by ¹H NMR analysis to be 0.30.This material is water soluble at greater than 0.1 wt %.

Inventive Polymer Example 9 (DoS=0.40)

Modification of Poly Alpha-1,6-Glucan with Dihydropyran

Poly alpha-1,6-glucan powder (56 kDa, 15-25% alpha-1,2-branching and75-85% alpha-1,6 linkages, 20.20 g) was dissolved in DMSO (100 mL) andstirred 85° C. for 30 minutes. The solution was cooled to 50° C.followed by the addition of HCl in dioxane (4.0 M, 1.0 mL) and thedropwise addition of dihydropyran (12.46 g). The reaction mixture wasstirred at 50° C. for 4 h. The product was precipitated and purifiedusing isopropanol yielding 26.28 g of a white powder after vacuumdrying.

Inventive Polymer Example 10 (DoS=0.20)

Modification of Poly Alpha-1,6-Glucan with Dihydropyran in DMSO

Glucan powder (40 k, 15-25% alpha-1,2-branching and 75-85% alpha-1,6linkages, 20.10 g) was dissolved in DMSO (100 mL) and stirred 85° C. for30 minutes. The solution was cooled to 50° C. followed by the additionof HCl in dioxane (4.0 M, 1.0 mL) and the dropwise addition ofdihydropyran (6.33 g). The reaction mixture was stirred at 50° C. for 5h. The product was precipitated and purified using isopropanol yielding25.25 g of a white powder after vacuum drying.

Inventive Polymer Example 11 (DoS=0.60)

Modification of Poly Alpha-1,6-Glucan with Dihydropyran in DMSO

Glucan powder (40 k, 15-25% alpha-1,2-branching and 75-85% alpha-1,6linkages, 20.11 g) was dissolved in DMSO (100 mL) and stirred 85° C. for30 minutes. The solution was cooled to 50° C. followed by the additionof HCl in dioxane (4.0 M, 1.0 mL) and the dropwise addition ofdihydropyran (18.82 g). The reaction mixture was stirred at 50° C. for5.5 h. The product was precipitated and purified using isopropanolyielding 22.97 g of a white powder after vacuum drying.

Inventive Polymer Example 12 (DoS=0.60)

Modification of Poly Alpha-1,6-Glucan with Dihydropyran in DMSO (WaterPrecipitated)

Glucan powder (17 k, 40% alpha-1,2-branching and 60% alpha-1,6 linkages20.12 g) was dissolved in DMSO (100 mL) and stirred 85° C. for 30minutes. The reaction mixture remained slightly opaque. The solution wascooled to 50° C. followed by the addition of HCl in dioxane (4.0 M, 1.0mL) and the dropwise addition of dihydropyran (18.86 g). The reactionmixture was stirred at 50° C. for 3.5 h. The product was precipitatedand purified using water yielding 14.33 g of a white powder after vacuumdrying.

Inventive Polymer Example 13 (DoS=0.60)

Modification of Poly Alpha-1,6-Glucan with Dihydropyran in DMSO (WaterPrecipitated)

Glucan powder (15.4 k, 10% alpha 1,3-branching and 90%alpha-1,6-linkages, 20.14 g) was dissolved in DMSO (100 mL) and stirred85° C. for 30 minutes. The solution was cooled to 50° C. followed by theaddition of HCl in dioxane (4.0 M, 1.0 mL) and the dropwise addition ofdihydropyran (18.85 g). The reaction mixture was stirred at 50° C. for 4h. The product was precipitated and purified using water yielding 22.91g of a white powder after vacuum drying.

Inventive Polymer Example 14 (DoS=0.60)

Modification of Poly Alpha-1,6-Glucan Poly Alpha-Glucan with MixedLinkage (1,3,6) with Longer Branching and (1,2) Branching (˜10%) withDihydropyran in DMSO (Water Precipitated)

Glucan powder (3.5 k, ˜10% 1,2-branching and mixed linkage (1,3,6),20.11 g) was dissolved in DMSO (100 mL) and stirred 85° C. for 30minutes. The solution was cooled to 50° C. followed by the addition ofHCl in dioxane (4.0 M, 1.0 mL) and the dropwise addition of dihydropyran(18.86 g). The reaction mixture was stirred at 50° C. for 5 h. Theproduct was precipitated and purified using water yielding 22.91 g of awhite powder after vacuum drying.

Inventive Polymer Example 15 (DoS=0.60)

Modification of Poly Alpha-1,6-Glucan with Dihydrofuran in DMSO

Glucan powder (40 k, 15-25% alpha-1,2-branching and 75-85% alpha-1,6linkage, 10.11 gram) was dissolved in DMSO (50 mL) and stirred 85° C.for 30 minutes. The solution was cooled to 50° C. followed by theaddition of HCl in dioxane (4.0 M, 0.5 mL) and the dropwise addition ofdihydrofuran (7.82 g). The reaction mixture was stirred at 50° C. for4.5 h. The product was precipitated and purified using isopropanolyielding 11.59 g of a white powder after vacuum drying.

Inventive Polymer Example 16 (DoS=0.65)

Modification of Poly Alpha-1,6-Glucan with Benzyl Chloride

Poly alpha-1,6-glucan (15 kDa, 9% alpha-1,2-branching and 91% alpha-1,6linkages, 415 g) was added to water (600 mL) portion by portion at roomtemperature with stirring. The mixture was stirred at room temperatureuntil solids were dissolved. Sodium hydroxide solution (236 g 50 wt %)was added to the solution at room temperature. The reaction mixture washeated to 75° C. and benzyl chloride (312 g) was added. The reactionmixture was stirred at 75-80° C. for 3 hours. The reaction mixture wasstirred at 75-80° C. for 3 hours. The reaction mixture was washed withwater (2×1200 mL) and adjusted the pH to about 7. The glue-like mass wasdivided into three portions and each was washed with IPA repeatedly(3×1000 mL). The resulting solid was collected and dried. The degree ofsubstitution was determined by ¹H NMR analysis to be 0.65.

Biodegradation Test Results

The biodegradability of the poly alpha-1,6-glucan derivatives ofExamples 1, and 8 were determined by following the OECD 301B ReadyBiodegradability CO₂ Evolution Test Guideline. In this study, the testsubstance is the sole carbon and energy source and under aerobicconditions microorganisms metabolize the test substance producing CO₂ orincorporating the carbon into biomass. The amount of CO₂ produced by thetest substance (corrected for the CO₂ evolved by the blank inoculum) isexpressed as a percentage of the theoretical amount of CO₂ (ThCO₂) thatcould have been produced if the organic carbon in the test substance wascompletely converted to CO₂.

TABLE 3 Biodegradation Test Results % ThCO₂ evolution PolysaccharideDerivative from at 56 Days Inventive polymer Example 1 43.2 ± 6.7Inventive polymer Example 8 66.9 ± 2.1

The biodegradation test results (Table 3) show the materials havedegraded by more than 40% at 56 days.

Polymer Performance in Liquid Detergent

Liquid detergents below are prepared by traditional means known to thoseof ordinary skill in the art by mixing the listed ingredients.

A: comparative composition, with no poly alpha-1,6-glucan derivative;

B: Inventive composition, with inventive poly alpha-1,6-glucanderivative;

C: Inventive composition, with inventive poly alpha-1,6-glucanderivative;

Com- parative Inventive Detergent Ingredient A B C Sodium Lauryl Sulfate(%) 11.09 11.09 11.09 C24EO9 (%) 7.58 7.58 7.58 C12/14 Amine Oxide (%)1.88 1.88 1.88 C1218 Fatty acid (%) 2.95 2.95 2.95 Silicone (%) 0.0050.005 0.005 NaOH (%) 1.64 1.64 1.64 Sodium Tetraborate (%) 0.96 0.960.96 Citric Acid (%) 2.45 2.45 2.45 Solvent (1,2-Propylene glycol) (%)11.89 11.89 11.89 Ethanol (%) 0.82 0.82 0.82 Enzymes (%) 0.08 0.08 0.08Sodium Formate (%) 0.07 0.07 0.07 Perfume (%) 0.45 0.45 0.45 Inventivepolymer Example 1 (%) 0.00 2.45 0.00 Inventive polymer Example 16 (%)0.00 0.00 2.45 Water Balance Balance Balance ΔWI(CIE) versus referenceon PE Reference 23.1 10.5 (100% polyester knit)

The whiteness maintenance performance of formulation comparativecomposition A, inventive composition B and inventive composition C areevaluated according to the whiteness method. Inventive polyalpha-1,6-glucan derivative can provide significant improvement onwhiteness performance compare with comparative composition A.

Biodegradation Data

Sample Backbone Modification % CO2 evolved Inventive polymer example 1Alpha-1,6, 10% Benzyl (0.26) 43.2% (56 days) branching, 17K Inventivepolymer example 8 Alpha-1,6, 10% allyl gylcidyl 66.9% (56 days)branching, 17K ether (0.3) Comparative polymer, example Alpha-1,6 Tosyl(0.2) 28% (28 days) 8 from US2020/002646 backbone, 25% SSO4 (0.5) 37.4%(54 days) branching, 17K Comparative polymer, example Alpha-1,3, 120KBenzyl (0.5) −2.5% (28 days) 13B from US2020/002646 —CH₂-COOH (0.5)Comparative polymer, example Alpha-1,6, 40% -COOH (0.7) −1.3% (28 days)7 from US2015/0232785 branching, 17K Comparative polymer, exampleAlpha-1,3,8 -COOH (0.5) 17% 7 from US2015/0232785 Comparative polymerfrom Alpha-1,6, 40% -COOH (0.9) −1.0% (70 days) US2019/136153 branching,17K -phenyl (0.8)

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. Itis thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A laundry care or dish care composition comprising a poly alpha-1,6-glucan derivative, wherein the poly alpha-1,6-glucan derivative comprises: (i) a poly alpha-1,6-glucan backbone of glucose monomer units, wherein about 40% or more of the glucose monomer units are linked via alpha-1,6 glycosidic linkages, and optionally at least about 5% of the backbone glucose monomer units have branches via alpha-1,2 and/or alpha-1,3 glycosidic linkages; (ii) at least about one hydrophobic organic group linked to the poly alpha-1,6-glucan backbone through an ether (—O—) linkage moiety; and (iii) one or more additional hydrophobic organic groups linked to the poly alpha-1,6-glucan backbone through linkage moiety selected from one or more of ester (—OCO—), carbamate

sulfonate ester (—OSO₂—), and carbonate ester (—OCOO—); wherein, the poly alpha-1,6-glucan backbone has a weight average degree of polymerization of at least about 5; wherein, the poly alpha-1,6-glucan derivative has a degree of substitution of ether linkage moiety of from about 0.20 to about 1.00; and wherein the poly alpha-1,6-glucan derivative is free from hydrophilic substitution.
 2. The composition according to claim 1, wherein no hydrophilic organic groups are linked to the poly alpha-1,6-glucan backbone through the ether (—O—) linkage moiety.
 3. The composition according to claim 1, wherein the alpha-1,6-glucan backbone of the poly alpha-1,6-glucan derivative has a weight average degree of polymerization of either about 5 to about 95, or about 125 to about
 4000. 4. The composition according to claim 1, wherein, the poly alpha-1,6-glucan derivative has a degree of substitution of ether linkage moiety of about 0.40 to about 0.90.
 5. The composition according to claim 1, wherein about 5% to about 9% or about 26% to about 40% of the backbone glucose monomer units have branches via alpha-1,2 and/or alpha-1,3 glycosidic linkages.
 6. The composition according to claim 1, wherein the hydrophobic organic group is a benzyl group, wherein the benzyl group may be substituted with one or more of: a halogen; a cyano group; an ester group; an amide group; an ether group; a C₁ to C₆ alkyl group; an aryl group; a C₂ to C₆ alkene group; a C₂ to C₆ alkyne group; or any combination thereof.
 7. The composition according to claim 1, wherein the composition is in the form of a liquid, a gel, a powder, a hydrocolloid, an aqueous solution, a granule, a tablet, a capsule, a single compartment sachet, a pad, a multi-compartment sachet, a single compartment pouch, or a multi-compartment pouch.
 8. The composition according to claim 1, wherein the composition further comprising an ingredient selected from: surfactant, an enzyme, a detergent builder, a complexing agent, a polymer, a soil release polymer, a surfactancy-boosting polymer, a bleaching agent, a bleach activator, a bleaching catalyst, a fabric conditioner, a clay, a foam booster, a suds suppressor, an anti-corrosion agent, a soil-suspending agent, an anti-soil re-deposition agent, a dye, a bactericide, a tarnish inhibitor, an optical brightener, a perfume, a saturated or unsaturated fatty acid, a dye transfer-inhibiting agent, a chelating agent, a hueing dye, a calcium cation, a magnesium cation, a visual signaling ingredient, an anti-foam, a structurant, a thickener, an anti-caking agent, a starch, sand, a gelling agent, or any combination thereof.
 9. The composition according to claim 1, wherein the composition comprises an enzyme selected from: a cellulase, a protease, an amylase, a lipase, or any combination thereof.
 10. The composition according to claim 1, wherein the poly alpha-1,6-glucan derivative is randomly substituted with the hydrophobic organic groups.
 11. The composition according to claim 1, wherein the glucose monomers of the poly alpha-1,6-glucan backbone are disproportionately substituted relative to the glucose monomers of any branches. 